Photosensitive resin composition, photosensitive resin laminate, and resist pattern formation method

Abstract

To provide a photosensitive resin composition which is excellent in independent thin line formability.SOLUTION: A photosensitive resin composition contains (A) an alkali-soluble polymer, (B) a compound having an ethylenic unsaturated bond, and (C) a polymerization initiator, wherein the component (A) contains a copolymer (A-1), the copolymer (A-1) has constitutional units derived from at least the following components: (a1) a (meth)acrylic acid, (a2) a styrene derivative, and (a3) a compound having an alcoholic hydroxy group and a (meth)acryloyl group, in the copolymer (A-1), the proportion of the constitutional unit derived from the component (a2) and the constitutional unit derived from the component (a3) is 50 to 80 mass%, and in the photosensitive resin composition, a ratio {content of component (A) / content of component (B)} of the content of the component (A) to the content of the component (B) is 1.40 or more and 2.00 or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition, a photosensitive resin laminate, a method for forming a resist pattern, and the like. [Background technology]

[0002] Printed wiring boards are generally produced using a photolithography method. In the photolithography method, a photosensitive resin layer (a layer containing a photosensitive resin composition) is first formed on a substrate. Then, the photosensitive resin layer is exposed to light and developed to form a resin pattern (resist pattern). Then, a conductor pattern is formed by etching or plating, and the resist pattern is removed to form a desired wiring pattern on the substrate.

[0003] In the photolithography method, the photosensitive resin layer is formed on the substrate by the following method: A method of applying a solution of a photosensitive resin composition onto a substrate and drying it; or A method for laminating a photosensitive resin layer of a dry film resist (a photosensitive resin laminate having a support and a photosensitive resin layer) onto a substrate; In the manufacturing process of electronic devices, for example, the manufacturing process of printed wiring boards, the method using a photosensitive resin laminate is often adopted.

[0004] Patent Document 1 describes a photosensitive resin composition containing a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and an anthracene-based sensitizer, wherein the binder polymer contains polymer (a), and the polymer (a) contains hydroxyalkyl (meth)acrylate units and 40 mass % or more of styrene or styrene derivative units. Patent Document 1 also describes a photosensitive resin laminate comprising a support and a photosensitive resin layer formed using the photosensitive resin composition. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2021 / 193232 Summary of the Invention [Problem to be solved by the invention]

[0006] In the photosensitive resin composition described in Patent Document 1, the polymer (a) contains 40% by mass or more of styrene or styrene derivative units from the viewpoint of adhesion.

[0007] On the other hand, in recent years, with the miniaturization and increasing density of electronic devices, there has been an increasing demand for wiring that is finer than before and has wider spacing between patterns (this type of wiring is called "independent fine wires"). Independent fine wires can be realized by satisfying a suitable balance between excellent adhesion between the substrate and the resist pattern and various properties (for example, flexibility of the cured film), but the formability of this type of independent fine wires has not been considered in prior art, including Patent Document 1. That is, how to provide a photosensitive resin composition that is excellent in the ability to form independent thin lines has been a problem that needs to be solved.

[0008] An object of the present invention is to provide a photosensitive resin composition that is excellent in the formability of independent thin lines (hereinafter, sometimes referred to as "independent thin line formability"). Another object of the present invention is to provide a photosensitive resin laminate obtained using such a photosensitive resin composition, a method for forming a resist pattern, and a method for forming a wiring board. [Means for solving the problem]

[0009] One aspect of the present invention is as follows. [1] Ingredients: (A) Alkali-soluble polymer; (B) a compound having an ethylenically unsaturated bond; and (C) a polymerization initiator; A photosensitive resin composition comprising: The component (A) contains a copolymer (A-1), The copolymer (A-1) contains at least the following components: (a1) (meth)acrylic acid; (a2) styrene derivatives; and (a3) a compound having an alcoholic hydroxy group and a (meth)acryloyl group; having a structural unit derived from the proportion of the structural units derived from the component (a2) and the structural units derived from the component (a3) ​​in the copolymer (A-1) is 50 to 80 mass %, The proportion of the structural units derived from the component (a2) in the copolymer (A-1) is greater than the proportion of the structural units derived from the component (a3) ​​in the copolymer (A-1), and In the photosensitive resin composition, the ratio of the content of the component (A) to the content of the component (B) {content of component (A) / content of component (B)} is 1.40 or more and 2.00 or less. Photosensitive resin composition. [2] 2. The photosensitive resin composition according to item 1, wherein the proportion of structural units derived from the component (a2) in the copolymer (A-1) is 30 to 70% by mass. [3] 3. The photosensitive resin composition according to item 1 or 2, wherein the proportion of structural units derived from the component (a1) in the copolymer (A-1) is 25 mass % or less. [4] 4. The photosensitive resin composition according to any one of items 1 to 3, wherein the copolymer (A-1) contains, as the component (a1), a structural unit derived from methacrylic acid. [5] 5. The photosensitive resin composition according to any one of items 1 to 4, wherein the proportion of structural units derived from methacrylic acid in the copolymer (A-1) is 15 to 25% by mass. [6] 6. The photosensitive resin composition according to any one of items 1 to 5, wherein the proportion of structural units derived from the component (a3) ​​in the copolymer (A-1) is 5% by mass or more. [7] In the copolymer (A-1), the proportion of structural units derived from the component (a1) is 15 to 25% by mass, The proportion of structural units derived from the component (a2) is 30 to 70 mass %, and 7. The photosensitive resin composition according to any one of items 1 to 6, wherein the proportion of structural units derived from the component (a3) ​​is 5 to 30 mass %. [8] The copolymer (A-1) further comprises the following component: (a4) The following general formula (I): [ka] (In the formula, R1 represents a hydrogen atom or a methyl group, and R2 represents an alkyl group having 3 or more carbon atoms.) Alkyl (meth)acrylate represented by the formula: having a structural unit derived from 8. The photosensitive resin composition according to any one of items 1 to 7, wherein the proportion of the structural units derived from the component (a4) in the copolymer (A-1) is 1% by mass to 15% by mass. [9] In the copolymer (A-1), the proportion of structural units derived from the component (a1) is 15 to 25% by mass, the proportion of structural units derived from the component (a2) is 30 to 70 mass %, The proportion of structural units derived from the component (a3) ​​is 5 to 30 mass %, and 9. The photosensitive resin composition according to item 8, wherein the proportion of structural units derived from the component (a4) is 1 to 15 mass %.

[10] Item 10. The photosensitive resin composition according to item 8 or 9, wherein R2 represents an alkyl group having 3 to 12 carbon atoms.

[11] 11. The photosensitive resin composition according to any one of items 8 to 10, wherein the component (a4) includes 2-ethylhexyl (meth)acrylate.

[12] 12. The photosensitive resin composition according to any one of items 1 to 11, wherein the copolymer (A-1) has a weight average molecular weight of 30,000 or more and 50,000 or less.

[13] 13. The photosensitive resin composition according to any one of items 1 to 12, wherein the copolymer (A-1) is contained in an amount of 10 mass % or more based on the total solid content of the photosensitive resin composition.

[14] 14. The photosensitive resin composition according to any one of items 1 to 13, wherein the copolymer (A-1) is contained in an amount of 30 mass % or more based on the total solid content of the photosensitive resin composition.

[15] 15. The photosensitive resin composition according to any one of items 1 to 14, wherein the component (B) contains a bifunctional (meth)acrylate compound in an amount of 20 mass% or more based on the total solid content of the photosensitive resin composition.

[16] Item 16. The photosensitive resin composition according to item 15, wherein the bifunctional (meth)acrylate compound includes a di(meth)acrylate having a bisphenol A structure.

[17] Item 17. The photosensitive resin composition according to item 16, wherein the di(meth)acrylate having a bisphenol A structure is contained in an amount of 20 mass% or more based on the total solid content of the photosensitive resin composition.

[18] 18. The photosensitive resin composition according to any one of items 1 to 17, wherein the ratio of the content of the component (A) to the content of the component (B) in the photosensitive resin composition {content of component (A) / content of component (B)} is 1.50 or more.

[19] 19. The photosensitive resin composition according to any one of items 1 to 18, wherein the ratio of the content of the component (A) to the content of the component (B) in the photosensitive resin composition {content of component (A) / content of component (B)} is 1.70 or less.

[20] 20. The photosensitive resin composition according to any one of items 1 to 19, wherein the component (C) includes a compound having a biimidazole structure. [twenty one] The photosensitive resin composition further contains a sensitizer, 21. The photosensitive resin composition according to any one of items 1 to 20, wherein the sensitizer comprises a compound having at least one skeleton selected from the group consisting of skeletons derived from pyrazoline derivatives, anthracene derivatives, naphthalene derivatives, and oxazole derivatives. [twenty two] 22. The photosensitive resin composition according to item 21, wherein the sensitizer comprises a compound having a skeleton derived from an anthracene derivative. [twenty three] 23. The photosensitive resin composition according to item 21 or 22, wherein the sensitizer comprises at least one compound selected from the group consisting of 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, and 10-phenyl-9-anthraceneboronic acid. [twenty four] 24. A photosensitive resin laminate comprising a support and a photosensitive resin layer containing the photosensitive resin composition according to any one of items 1 to 23. [twenty five] The following method: (1) After forming the photosensitive resin layer on a flexible substrate, the layer is exposed to light with an energy amount that leaves 15 steps on a Stouffer Industries 41-step step tablet, with a width of 1 inch and a length of 250 mm, to obtain a cured film on the substrate. (2) The exposed substrate is developed using a 1% by mass Na2CO3 aqueous solution at 30°C for twice the shortest development time. (3) After development, the substrate is washed with water for twice the minimum development time. (4) After washing with water, the substrate is cut into a 1.2 inch wide piece so that the 1 inch wide cured photosensitive resin layer is located in the center of the width direction, thereby obtaining a sample. (5) Cylindrical Mandrel Method A mandrel test in accordance with the method of JIS K5600-5-1 is carried out on the sample. (6) The smallest mandrel diameter at which cracks are not observed in the cured film, or the smallest mandrel diameter at which peeling of the cured film from the substrate is not observed, is determined. 25. The photosensitive resin laminate according to item 24, wherein the smallest mandrel diameter, as determined by

[26] Item 26. The photosensitive resin laminate according to Item 24 or 25, wherein the photosensitive resin layer has a thickness of 10 to 50 μm.

[27] the photosensitive resin laminate includes a protective layer on the opposite side of the photosensitive resin layer from the support, 27. The photosensitive resin laminate according to any one of items 24 to 26, wherein the protective layer is a polyethylene terephthalate (PET) film or a biaxially oriented polypropylene (OPP) film.

[28] Item 28. The photosensitive resin laminate according to item 27, wherein the protective layer has a release layer on a surface thereof.

[29] a lamination step of laminating the photosensitive resin layer in the photosensitive resin laminate according to any one of Items 24 to 28 onto a substrate; an exposure step of exposing the photosensitive resin layer of the photosensitive resin laminate; and a development step of removing unexposed areas of the photosensitive resin layer; A method for forming a resist pattern, comprising:

[30] forming a resist pattern on a substrate using the photosensitive resin laminate according to any one of items 24 to 28; forming a conductive pattern by etching or plating the substrate on which the resist pattern has been formed; peeling the resist pattern from the substrate; A method for forming a wiring board, comprising:

[31] A photosensitive resin laminate having a support and a photosensitive resin layer containing a photosensitive resin composition, The photosensitive resin composition comprises the following components: (A) Alkali-soluble polymer; (B) a compound having an ethylenically unsaturated bond; and (C) a polymerization initiator; Including, The copolymer (A-1) contains at least the following components: (a1) (meth)acrylic acid; (a2) styrene derivatives; and having a structural unit derived from The content of the (a2) component is 25% by mass or more. Photosensitive resin laminate.

[32] The following method: (1) After forming the photosensitive resin layer on a flexible substrate, the layer is exposed to light with an energy amount that leaves 15 steps on a Stouffer Industries 41-step step tablet, with a width of 1 inch and a length of 250 mm, to obtain a cured film on the substrate. (2) The exposed substrate is developed using a 1% by mass Na2CO3 aqueous solution at 30°C for twice the shortest development time. (3) After development, the substrate is washed with water for twice the minimum development time. (4) After washing with water, the substrate is cut into a 1.2 inch wide piece so that the 1 inch wide cured photosensitive resin layer is located in the center of the width direction, thereby obtaining a sample. (5) Cylindrical Mandrel Method A mandrel test in accordance with the method of JIS K5600-5-1 is carried out on the sample. (6) The smallest mandrel diameter at which cracks are not observed in the cured film, or the smallest mandrel diameter at which peeling of the cured film from the substrate is not observed, is determined. Item 32. The photosensitive resin laminate according to item 31, wherein the smallest mandrel diameter, as determined by

[33] Item 33. The photosensitive resin laminate according to item 32, wherein the smallest mandrel has a diameter of 6 mm or less.

[34] 34. The photosensitive resin laminate according to any one of items 31 to 33, wherein the shortest development time when a 1 mass % Na2CO3 aqueous solution at 30°C is sprayed onto the photosensitive resin layer for a predetermined time is 0.6 to 1.1 seconds per 1 μm of film thickness.

[35] 35. The photosensitive resin laminate according to any one of items 31 to 34, wherein the photosensitive resin layer has a thickness of 10 to 50 μm. [Effects of the Invention]

[0010] According to the first aspect of the present invention, it is possible to provide a photosensitive resin composition that is excellent in the ability to form independent thin lines. According to a preferred embodiment of the first aspect of the present invention, a photosensitive resin composition can be provided that can obtain a photosensitive resin layer that is excellent in developability and can form a resist pattern that is excellent in at least one or all of resolution and flexibility. Furthermore, according to the first aspect of the present invention, it is possible to provide a photosensitive resin laminate having the photosensitive resin layer, a method for forming a resist pattern, and a method for forming a wiring board.

[0011] According to the second aspect of the present invention, it is possible to provide a photosensitive resin laminate that is excellent in the ability to form independent thin lines. According to a preferred embodiment of the second aspect of the present invention, it is also possible to provide a photosensitive resin laminate that is capable of forming a resist pattern with excellent resolution. Furthermore, according to a second aspect of the present invention, it is possible to provide a method for forming a resist pattern and a method for forming a wiring board using the photosensitive resin laminate. [Brief explanation of the drawings]

[0012] [Figure 1] FIG. 2 is a plan view showing the configuration of a drawing pattern related to this embodiment. [Figure 2] FIG. 2 is a plan view showing the configuration of a drawing pattern related to this embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0013] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to the accompanying drawings, in which: FIG.

[0014] In the present specification, when a plurality of structures represented by the same symbol exist in the same formula, the structures may be independently selected and may be the same or different from each other, unless otherwise specified. When a plurality of structures represented by the same symbol exist in different formulas, the structures may be independently selected and may be the same or different from each other, unless otherwise specified. In the present specification, various measurements are carried out based on the methods described in the Examples unless otherwise specified. In the present specification, the upper or lower limit of a numerical range described in a stepwise manner may be replaced by the upper or lower limit of a corresponding numerical range described in another stepwise manner, and may further be replaced by the corresponding value described in the Examples.

[0015] In this specification, "(meth)acrylic" means "acrylic" and / or "methacrylic", "(meth)acrylate" means "acrylate" and / or "methacrylate", and "(meth)acryloyl" means "acryloyl" and / or "methacryloyl". A "compound containing a (meth)acryloyl group" is referred to as, for example, a "(meth)acrylate compound". In this specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes, as long as the function of the process is achieved. In the contents shown in the drawings, the scale, shape, and length may be exaggerated for clarity.

[0016] As used herein, the term "derivative" includes not only compounds derived from a parent compound (compounds other than the parent compound) but also the parent compound itself. Thus, for example, a "styrene derivative" includes not only compounds derived from styrene (compounds other than styrene) but also styrene itself, which is the parent compound itself.

[0017] The following describes embodiments of the present invention, and the effects achieved by these embodiments are related to the effects of the present invention. In one aspect, unless otherwise specified: "Adhesion" refers to the adhesiveness between the resist pattern and the substrate; "Resolution" refers to the resolution performance of the resist pattern; "Developability" refers to the development performance of the photosensitive resin layer (resist); "Flexibility of the cured film" refers to the flexibility of the photosensitive resin layer (resist), particularly the photosensitive resin layer cured by exposure; Each means:

[0018] [First embodiment] [Photosensitive resin composition] One aspect of this embodiment is a photosensitive resin composition. Such a photosensitive resin composition comprises the following components: (A) Alkali-soluble polymer; (B) a compound having an ethylenically unsaturated bond; and (C) a polymerization initiator; In the photosensitive resin composition, The component (A) contains a copolymer (A-1), The copolymer (A-1) contains at least the following components: (a1) (meth)acrylic acid; (a2) styrene derivatives; and (a3) a compound having an alcoholic hydroxy group and a (meth)acryloyl group; having a structural unit derived from the proportion of the structural units derived from the component (a2) and the structural units derived from the component (a3) ​​in the copolymer (A-1) is 50 to 80 mass %, The proportion of the structural units derived from the component (a2) in the copolymer (A-1) is greater than the proportion of the structural units derived from the component (a3) ​​in the copolymer (A-1), and In the photosensitive resin composition, the ratio of the content of the component (A) to the content of the component (B) {content of component (A) / content of component (B)} is 1.40 or more and 2.00 or less. Such a photosensitive resin composition has excellent independent fine line forming properties. Furthermore, a preferred embodiment of the photosensitive resin composition can form a photosensitive resin layer (resist) that is excellent in at least one, at least two, or all of resolution, developability, and cured film flexibility. Furthermore, such a photosensitive resin composition can provide a photosensitive resin laminate having the photosensitive resin layer, a method for forming a resist pattern, and the like.

[0019] The present inventors have found that by employing one embodiment of the present invention, a photosensitive resin composition with excellent independent fine line formability can be obtained. While a photosensitive resin layer is cured in an exposure step, the cured photosensitive resin layer (cured film) is often required to have a certain degree of flexibility. According to one embodiment of the present invention, a photosensitive resin composition capable of forming a resist pattern that satisfies a favorable balance between adhesion and various properties (e.g., flexibility of the cured film) can be provided. Here, in one embodiment of the present invention, when the flexibility of the cured film is excellent, not only is the flexibility of the cured film high, but the cured film also satisfies a favorable balance between hardness and softness.

[0020] In this specification, the above components (A) to (C) may be simply referred to as "component (A)" to "component (C)." The same applies to the components other than components (A) to (C), which will be described later. Each component and the raw materials for each component may be used alone or in combination of two or more. In this specification, the "solid content" of the photosensitive resin composition means the components of the photosensitive resin composition other than the solvent. Each component will be described below.

[0021] <Component (A)> ≪Schematic configuration≫ The component (A) is a polymer that is soluble in an alkaline aqueous solution, and such a polymer is, for example, a vinyl polymer containing a carboxyl group. Component (A) preferably contains a carboxyl group and has an acid equivalent of 100 to 600. The acid equivalent refers to the mass in grams of an alkali-soluble polymer having one equivalent of a carboxyl group. Adjusting the acid equivalent to 100 or more is preferred from the viewpoint of excellent resolution and adhesion. Adjusting the acid equivalent to 600 or less is preferred from the viewpoint of excellent developability and strippability. The acid equivalent may be measured by potentiometric titration using a titrator (e.g., Hiranuma Automatic Titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd.) and 0.1 mol / L sodium hydroxide. From the same viewpoints as above, the acid equivalent of component (A) is more preferably 250 to 450.

[0022] The weight-average molecular weight (Mw) of component (A) is preferably 5,000 to 500,000. Adjusting the weight-average molecular weight (Mw) to 5,000 or more is preferred from the viewpoint of excellent performance, such as adhesion, flexibility of the cured film, and edge fuse property. Adjusting the weight-average molecular weight (Mw) to 500,000 or less is preferred from the viewpoint of easily preventing polymer aggregates from growing in size in the developer and, in turn, easily preventing yield reductions that may occur due to such aggregates during circuit board formation, etc. Here, edge fuse property refers to the ability to suppress the phenomenon in which the photosensitive resin layer protrudes from the edge of the roll when the photosensitive resin laminate is wound into a roll. The weight-average molecular weight (Mw) of component (A) is more preferably 20,000 to 70,000, even more preferably 30,000 to 50,000, and particularly preferably 35,000 to 45,000.

[0023] The polydispersity of the component (A) {weight average molecular weight (Mw) / number average molecular weight (Mn)} is preferably from 1.0 to 6.0, more preferably from 1.0 to 5.0, even more preferably from 1.0 to 4.0, and particularly preferably from 1.0 to 3.0.

[0024] The component (A) preferably has a monomer component consisting of a first monomer described below, and more preferably has a monomer component consisting of at least one type of the first monomer and at least one type of the second monomer described below.

[0025] The first monomer is an acidic monomer having a polymerizable unsaturated group in the molecule, such as a carboxylic acid or an acid anhydride having one polymerizable unsaturated group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. Among these, (meth)acrylic acid is preferred.

[0026] The content of the first monomer is preferably 10 to 50% by mass based on the total mass of all monomer components. Adjusting the content of the first monomer to 10% by mass or more is preferred from the viewpoint of excellent adhesion and resolution, and is more preferably 15% by mass or more, 18% by mass or more, or 21% by mass or more, even more preferably 23% by mass or more, and particularly preferably 25% by mass or more. Adjusting the content of the first monomer to 50% by mass or less is preferred from the viewpoint of excellent adhesion and resolution, and is more preferably 35% by mass or less, more preferably 30% by mass or less, even more preferably 29% by mass or less, and particularly preferably 27% by mass or less. When two or more first monomers are used, the total content of each is preferably within the above range.

[0027] The second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in the molecule, and examples of the second monomer include styrene derivatives, (meth)acrylate compounds having a hydroxy group, alkyl (meth)acrylates, (meth)acrylate compounds having an alicyclic or aromatic ring, vinyl alcohol, vinyl acetate, and (meth)acrylonitrile esters.

[0028] Examples of styrene derivatives include styrene, oxystyrene, acetoxystyrene, alkylstyrene, and halogenoalkylstyrene.

[0029] Examples of the (meth)acrylate compound having a hydroxy group include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and glycerin mono(meth)acrylate.

[0030] Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

[0031] Examples of (meth)acrylate compounds having an alicyclic or aromatic ring include benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, phenoxyethyl (meth)acrylate, and ethyl carbitol (meth)acrylate.

[0032] In this embodiment, the component (A) may be used alone or in combination of two or more. When two or more types are used in combination, the molecular weights and polydispersities of the monomers in the multiple components (A) are preferably selected so that the weighted average value, when the content ratio is treated as the weight, falls within the above range.

[0033] The synthesis of component (A) is preferably carried out by mixing an appropriate amount of a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile with a solution prepared by diluting one or more of the monomers described above with a solvent such as acetone, methyl ethyl ketone, or isopropanol, followed by heating and stirring. The synthesis may be carried out by adding a portion of the mixture dropwise to the reaction solution. Alternatively, after the reaction is complete, additional solvent may be added to adjust the concentration to the desired level. In addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may also be used as a synthesis method. Alternatively, the synthesis may be carried out by living radical polymerization.

[0034] The content of component (A) may be 30% by mass or more, 35% by mass or more, 40% by mass or more, or 45% by mass or more, based on the total solid content of the photosensitive resin composition. From the viewpoint of optimally achieving the effects of the present invention, the content of component (A) is preferably 50% by mass or more, more preferably 55% by mass or more, based on the total solid content of the photosensitive resin composition. Furthermore, the content is 70% by mass or less, preferably 65% ​​by mass or less, or 60% by mass or less.

[0035] In order to obtain a photosensitive resin composition having excellent desired properties, it is preferable to control the mass ratio of the (A) component to the (B) component {(A) component / (B) component; sometimes abbreviated as "A / B"} within a predetermined range. Controlling the A / B value to a large value tends to be advantageous in terms of excellent resolution and adhesion, while controlling the A / B value to a small value tends to be advantageous in terms of excellent developability and flexibility of the cured film. A / B can be controlled by adjusting the charge ratio of the (A) component to the (B) component when preparing the photosensitive resin composition. A / B can be analyzed from the photosensitive resin layer using a predetermined method, and the value obtained thereby is based on the above charge ratio when preparing the photosensitive resin composition. The analysis of the A / B value can be carried out, for example, by the following steps: (1) After dissolving the photosensitive resin layer in a good solvent, a poor solvent for only component (A) is added dropwise to separate component (A) by reprecipitation, and the mass of component (A) obtained by reprecipitation is measured. (2) The other components such as the initiator are individually quantified using GC-MS or the like, and the mass of component (B) is indirectly determined by measuring the contents of components other than component (A) and component (B), and the value of A / B is calculated from this. This can be done by

[0036] By controlling the A / B value of the photosensitive resin composition of this embodiment to 1.40 or more, it is easy to provide a photosensitive resin layer that satisfies high levels of developability, resolution, adhesion, and flexibility of the cured film. From the same viewpoint, the A / B value is more preferably 1.50 or more. The upper limit of the A / B value is preferably 2.00 or less, more preferably 1.80 or less, and even more preferably 1.70 or less.

[0037] When component (A) contains a copolymer containing a large amount of styrene as a monomer component, the photosensitive resin composition containing component (A) tends to have excellent resolution and adhesion. In order to achieve this effect, if the content of component (A) in a photosensitive resin composition containing a copolymer containing a large amount of styrene as a monomer component is increased (e.g., A / B is 1.40 or more), the cured film and resist pattern tend to become hard and brittle. It has generally been recognized that this makes it difficult to form a thin resist pattern and, conversely, tends to result in poor adhesion. On the other hand, according to this embodiment, a photosensitive resin layer (resist) can be provided that exhibits excellent flexibility of the cured film even when using a photosensitive resin composition containing a copolymer containing a large amount of styrene as a monomer component. It is precisely because of this photosensitive resin composition that controlling the A / B value to 1.40 or more facilitates the provision of a photosensitive resin layer that satisfies high levels of developability, resolution, adhesion, and cured film flexibility.

[0038] In the present disclosure, when component (A) contains multiple types of copolymers, the glass transition temperature Tg of component (A) is the weight average Tg total It is expressed as: Such weight average Tg total is expressed by the following formula: Tg total = Σi (W i ×Tg i ) / W total (In the formula, W i is the solid weight of each alkali-soluble polymer, and Tg i is the glass transition temperature (Tg) of each alkali-soluble polymer calculated by the Fox equation, and W total is the total solid weight of each alkali-soluble polymer. This is the value obtained according to This Tg total From the viewpoint of excellent developability and flexibility of the cured film, the value of Tg is preferably 100°C or less. total From the same viewpoint as above, Tg is more preferably 99°C or less, and even more preferably 95°C or less. total From the viewpoint of easy control of edge fusing properties, the temperature is preferably 50°C or higher, more preferably 70°C or higher, even more preferably 80°C or higher, and particularly preferably 85°C or higher.

[0039] ≪Copolymer (A-1)≫ The copolymer (A-1) contains at least the following components: (a1) (meth)acrylic acid; (a2) styrene derivatives; and (a3) a compound having an alcoholic hydroxy group and a (meth)acryloyl group; having a structural unit derived from the proportion of the structural units derived from the component (a2) and the structural units derived from the component (a3) ​​in the copolymer (A-1) is 50 to 80 mass %, The proportion of the structural units derived from the component (a2) in the copolymer (A-1) is greater than the proportion of the structural units derived from the component (a3) ​​in the copolymer (A-1), and In the photosensitive resin composition, the ratio of the content of the component (A) to the content of the component (B) {content of component (A) / content of component (B)} is 1.40 or more and 2.00 or less.

[0040] The weight average molecular weight (Mw) of the copolymer (A-1) is preferably from 20,000 to 70,000, more preferably from 30,000 to 50,000, and even more preferably from 35,000 to 45,000, from the viewpoint of excellent flexibility of the cured film.

[0041] From the viewpoint of suitably exerting the effects of the present invention, the content of copolymer (A-1) is preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and particularly preferably 45% by mass or more, based on the total solid content of the photosensitive resin composition.

[0042] From the viewpoint of optimally exerting the effects of the present invention, the content of copolymer (A-1) is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, and particularly preferably 80% by mass or more, based on the total weight of component (A). The content of copolymer (A-1) may be 100% by mass based on the total weight of component (A).

[0043] In the copolymer (A-1), the proportion of structural units derived from the component (a1) is 15 to 25% by mass, The proportion of structural units derived from the component (a2) is 30 to 70 mass %, and the proportion of structural units derived from the component (a3) ​​is 5 to 30 mass %; This makes it easier to obtain the effects of each of the components (a1) to (a3), and therefore makes it easier to achieve the effects of this embodiment. In the copolymer (A-1), The proportion of structural units derived from the following component (a4) is 1 to 15 mass %: This makes it easier to obtain the effects of each of the components (a1) to (a4), and therefore makes it easier to achieve the effects of this embodiment.

[0044] <Glass transition temperature (Tg)> The glass transition temperature (Tg) of the copolymer (A-1), calculated based on Fox's formula, is preferably 100°C or lower, from the viewpoint of excellent developability and flexibility of the cured film. From the same viewpoints as above, Tg is preferably 99°C or lower, and more preferably 95°C or lower. From the viewpoint of easy control of edge fusing properties, Tg is preferably 50°C or higher, more preferably 70°C or higher, even more preferably 80°C or higher, and particularly preferably 85°C or higher. The Tg of the copolymer (A-1) can be controlled by the types and proportions of the monomers constituting the copolymer (A-1), etc. By including the preferred components in the copolymer (A-1) in the preferred proportions, a preferred Tg can be easily achieved.

[0045] For a copolymer consisting of n kinds of monomers, the Fox formula for calculating the Tg (K: Kelvin) of the copolymer is as follows:

number

[0046] In this specification, the Tg value of a homopolymer consisting of monomers that form an alkali-soluble polymer is the literature value (Brandrup, J. Immergut, EH, ed., Polymer Handbook, Third Edition, John Wiley & Sons, 1989, Chapter VI "GLASS transition temperatures of polymers", p. 209). The glass transition temperature (Tg i ) is as follows:

[0047] [Table 1]

[0048] Based on the above [Equation 1] and [Table 1], for example, the Tg of the component (A) exemplified below can be derived as follows. Methacrylic acid / styrene / 2-hydroxyethyl methacrylate / 2-ethylhexyl acrylate (mass ratio=20 / 40 / 30 / 10):Tg 90℃ (mass ratio=20 / 45 / 25 / 10):Tg 91℃ (mass ratio=25 / 45 / 20 / 10):Tg 96℃ (Mass ratio=25 / 30 / 30 / 15):Tg 83℃ (mass ratio=20 / 40 / 25 / 15):Tg 79℃ (mass ratio=25 / 35 / 25 / 15):Tg 83℃ Methacrylic acid / styrene / 2-hydroxyethyl methacrylate / benzyl methacrylate (mass ratio = 27 / 39 / 4 / 30): Tg 110°C Methacrylic acid / benzyl methacrylate (mass ratio = 20 / 80): Tg 78°C Methacrylic acid / benzyl methacrylate / methyl methacrylate (mass ratio = 20 / 65 / 15): Tg 104°C

[0049] The mechanism by which the present embodiment has excellent properties is presumed to be as follows. When the component (A) contains a copolymer containing a relatively large amount (for example, 25% by mass or more and less than 80% by mass) of structural units derived from the component (a2), the resulting photosensitive resin composition tends to have excellent resolution and adhesion. On the other hand, because component (a2) is highly hydrophobic, it is necessary to improve the developability of the resulting photosensitive resin composition. Furthermore, since a photosensitive resin layer obtained using a photosensitive resin composition containing this copolymer tends to become a hard and brittle cured film after exposure, it is necessary to improve the flexibility of the cured film in order to ensure the formability of independent fine lines.

[0050] Here, component (a3) ​​exhibits high hydrophilicity. On the other hand, by making the proportion of structural units derived from component (a2) in copolymer (A-1) greater than the proportion of structural units derived from component (a3), it is possible to obtain a photosensitive resin composition that can balance various properties and form a photosensitive resin layer with excellent developability. In the photosensitive resin composition, by adjusting the contents of the components (a1) to (a3) ​​within the preferred ranges and further adjusting the Tg of the copolymer to 100°C or less, it is easy to obtain a photosensitive resin layer that can form a cured film with excellent flexibility.

[0051] <Component (a1)> The component (a1) is (meth)acrylic acid. The component (a1) may contain or consist of only either methacrylic acid or acrylic acid, or may contain or consist of both. When the component (a1) consists of only both methacrylic acid and acrylic acid, the copolymerization ratio of the component (a1) is determined by the sum of the copolymerization ratio of methacrylic acid and the copolymerization ratio of acrylic acid.

[0052] The proportion of structural units derived from component (a1) is 15 to 25% by mass, based on the total mass of all structural units in copolymer (A-1). Adjusting this proportion to 15% by mass or more is preferred from the viewpoints of excellent developability and resolution. Adjusting this proportion to 25% by mass or less is preferred from the viewpoints of controlling the glass transition temperature (Tg) of the photosensitive resin layer within an appropriate range and of the flexibility of the cured film. The proportion is more preferably 17 to 25% by mass, and even more preferably 18 to 23% by mass.

[0053] From the viewpoint of excellent resolution, the component (a1) preferably contains methacrylic acid. In this case, the copolymerization ratio of methacrylic acid is preferably 50% by mass or more, more preferably 75% by mass or more, and even more preferably 90% by mass or more, and may be 100% by mass, based on the entire component (a1). When the component (a1) contains methacrylic acid, the copolymerization ratio of methacrylic acid is preferably 15 to 25% by mass, and more preferably 17 to 23% by mass.

[0054] ≪(a2) component≫ The component (a2) is a styrene derivative. Examples of the component (a2) include styrene, oxystyrene, hydroxystyrene, acetoxystyrene, alkylstyrene, and halogenoalkylstyrene. Among these, the component (a2) preferably contains styrene.

[0055] The proportion of structural units derived from component (a2) is 25% by mass or more and less than 80% by mass, based on the total mass of all structural units in copolymer (A-1). This proportion may be, for example, 30 to 70% by mass. Adjusting this proportion to 25% by mass or more, for example 30% by mass or more, is preferred from the viewpoint of excellent resolution and adhesion. Adjusting this proportion to 70% by mass or less is preferred from the viewpoint of excellent developability and flexibility of the cured film. This proportion is preferably 30 to 60% by mass, more preferably 35 to 50% by mass.

[0056] Component (a2) may consist of only one compound, or may contain two or more compounds. When component (a2) contains two or more compounds, the copolymerization ratio of component (a2) is determined by the sum of the copolymerization ratios of the individual compounds.

[0057] ≪(a3) component≫ The component (a3) ​​is a compound having an alcoholic hydroxy group and a (meth)acryloyl group. The component (a3) ​​is a compound in which the hydrogen atom of the alkyl group of an alkyl (meth)acrylate is substituted with a hydroxy group. Examples of such compounds include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate. Among these, the component (a3) ​​preferably contains hydroxyethyl (meth)acrylate from the viewpoint of excellent developability.

[0058] Furthermore, the component (a3) ​​can be glycerin mono(meth)acrylate. Commercially available glycerin mono(meth)acrylate products include Blemmer (registered trademark) GLM, GLM-EX, and GLM-R (all trade names, manufactured by NOF Corporation).

[0059] The proportion of structural units derived from component (a3) ​​is 5 to 35% by mass, based on the total mass of all structural units in copolymer (A-1). Adjusting this proportion to 5% by mass or more is preferred from the viewpoint of achieving both developability and flexibility of the cured film. Adjusting this proportion to 35% by mass or less is preferred from the viewpoint of achieving excellent resolution and adhesion. This proportion is preferably 16% by mass or more, for example, 20 to 30% by mass, and more preferably 23 to 27% by mass.

[0060] The component (a3) ​​may consist of only one compound, or may contain two or more compounds. When the component (a3) ​​contains two or more compounds, the copolymerization ratio of the component (a3) ​​is determined by the sum of the copolymerization ratios of the individual compounds.

[0061] ≪(a4) component≫ The copolymer (A-1) may further contain, in addition to the structural units derived from the above components (a1) to (a3), a structural unit derived from the following component (a4), which is different from the above components (a1) to (a3).

[0062] Examples of the component (a4) include: (a4) The following general formula (I): [ka] (In the formula, R1 represents a hydrogen atom or a methyl group, and R2 represents an alkyl group having 3 or more carbon atoms.) Alkyl (meth)acrylates represented by the following formula are preferred. Generally, the glass transition temperature Tg of the homopolymer of component (a4) i is the glass transition temperature Tg of the homopolymer of component (a1), component (a2), or component (a3). i Since the glass transition temperature Tg of the copolymer (A-1) is lower than that of the copolymer (A-2), the use of such a component (a4) makes it easy to adjust the glass transition temperature Tg of the copolymer (A-1) to a low value.

[0063] As the component (a4), a compound represented by the above general formula (I) in which R2 is an alkyl group having 3 to 12 carbon atoms is preferred. Examples of such compounds include propyl(meth)acrylate, n-butyl(meth)acrylate, i-butyl(meth)acrylate, pentyl(meth)acrylate, hexyl(meth)acrylate, heptyl(meth)acrylate, octyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and nonyl(meth)acrylate. Of these, as the component (a4) represented by the above formula (I), a compound in which R2 is an alkyl group having 4 to 10 carbon atoms is more preferred, and a compound in which R2 is an alkyl group having 6 to 9 carbon atoms is even more preferred. As such a compound, 2-ethylhexyl(meth)acrylate is particularly preferred.

[0064] The proportion of structural units derived from component (a4) is preferably 1 to 15% by mass, based on the total mass of all structural units in copolymer (A-1). From the viewpoints of easily lowering the Tg of copolymer (A-1) and providing excellent flexibility to the cured film, this proportion is preferably 1% by mass or more. On the other hand, component (a4) has an unsaturated hydrocarbon group without a hydrophilic group, and therefore is highly hydrophobic. Furthermore, since component (a4) does not have an aromatic ring, it is preferable to balance it with component (a2), which has an aromatic ring incorporated into the polymer main chain. In this case, from the viewpoint of excellent properties (e.g., resolution, adhesion, developability, etc.), this proportion is preferably 15% by mass or less. This proportion is more preferably 5 to 13% by mass, and even more preferably 8 to 12% by mass.

[0065] <Monomers other than components (a1) to (a4)> Copolymer (A-1) may contain a monomer other than components (a1) to (a4) as a copolymerization component. The monomer other than components (a1) to (a4) is a first monomer other than (a1) or a second monomer other than components (a2) to (a4), and examples thereof include compounds exemplified above as the first monomer and the second monomer that do not fall under the category of components (a1) to (a4).

[0066] When the copolymer (A-1) contains a first monomer other than the component (a1), the copolymerization ratio of the total first monomers (including the component (a1)) is preferably 26% by mass or less, more preferably 25% by mass or less, from the viewpoint of excellent flexibility of the cured film. The copolymerization ratio of the first monomers other than the component (a1) may be 0% by mass.

[0067] When the copolymer (A-1) contains a second monomer other than the components (a2) to (a4), the copolymerization ratio of the monomer component is preferably 20% by mass or less, more preferably 10% by mass or less, from the viewpoint of easily achieving the effects of the present invention. The copolymerization ratio of the second monomer other than the components (a2) to (a4) may be 0% by mass.

[0068] <(B) component> Component (B) is a compound having an ethylenically unsaturated bond. Component (B) can have at least one ethylenically unsaturated bond per molecule. From the viewpoint of obtaining a photosensitive resin layer with appropriate flexibility, component (B) preferably contains a compound having two ethylenically unsaturated bonds per molecule. From the viewpoint of excellent crosslinking efficiency in the exposure step, component (B) may further contain a compound having three ethylenically unsaturated bonds per molecule, or may further contain a compound having four, five, or six ethylenically unsaturated bonds per molecule.

[0069] From the viewpoint of excellent resolution and adhesion, the content of the compound having two ethylenically unsaturated bonds in one molecule in component (B) is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, based on the total weight of component (B). This content may be 100% by mass or less, based on the total weight of component (B).

[0070] From the viewpoint of excellent resolution and adhesion, the content of the compound having two ethylenically unsaturated bonds in one molecule in the entire photosensitive resin composition is preferably 15% by mass or more, more preferably 20% by mass or more, and even more preferably 25% by mass or more, based on the total solid content in the photosensitive resin composition, and may be 40% by mass or less, based on the total solid content in the photosensitive resin composition.

[0071] When component (B) contains a compound having three or more ethylenically unsaturated bonds in one molecule, from the viewpoint of excellent adhesion and developability, the content of the compound having three or more ethylenically unsaturated bonds in one molecule is preferably 30% by mass or less, and may be 20% by mass or less, based on the total weight of component (B). Also, the content may be 1% by mass or more, and may be 5% by mass or more, based on the total weight of component (B).

[0072] Component (B) preferably contains a (meth)acrylate compound, and more preferably contains a bifunctional or higher functional (meth)acrylate compound (a compound having two or more (meth)acryloyl groups in one molecule) from the viewpoint of obtaining a photosensitive resin layer with appropriate flexibility. Regarding component (B), "a (meth)acrylate compound having n (meth)acryloyl groups in one molecule" is referred to as, for example, "n-functional." Regarding component (B), for example, having 1, 2, 3, 4, 5, or 6 ethylenically unsaturated bonds in one molecule is referred to as "monofunctional (or monofunctional)," "bifunctional," "trifunctional," "tetrafunctional," "pentafunctional," or "hexafunctional," respectively.

[0073] When component (B) contains a (meth)acrylate compound, from the viewpoint of excellent crosslinking efficiency in the exposure step, it may contain only a difunctional (meth)acrylate compound, or it may contain a difunctional (meth)acrylate compound and a trifunctional or higher functional (meth)acrylate compound. Component (B) may contain, for example, a tetrafunctional, pentafunctional, or hexafunctional (meth)acrylate compound together with or separately from the difunctional (meth)acrylate compound and / or the trifunctional or higher functional (meth)acrylate compound.

[0074] When component (B) contains a (meth)acrylate compound, the content of the bifunctional (meth)acrylate compound is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, based on the total mass of component (B), from the viewpoint of excellent resolution and flexibility of the cured film. Furthermore, the content may be 100% by mass or less, based on the total mass of component (B).

[0075] From the viewpoint of excellent resolution and adhesion, the content of the bifunctional (meth)acrylate compound in the entire photosensitive resin composition is preferably 15% by mass or more, more preferably 20% by mass or more, and even more preferably 25% by mass or more, based on the total solid content in the photosensitive resin composition, and may be 40% by mass or less, based on the total solid content in the photosensitive resin composition.

[0076] When component (B) contains a trifunctional or higher functional (meth)acrylate compound, from the viewpoint of excellent adhesion and developability, the content of the trifunctional or higher functional (meth)acrylate compound is preferably 30% by mass or less, or may be 20% by mass or less, based on the total weight of component (B), and may be 1% by mass or more, or may be 5% by mass or more, based on the total weight of component (B).

[0077] Examples of bifunctional (meth)acrylate compounds include alkyl di(meth)acrylate, 1,3-bis(meth)acryloyloxy-2-propanol, polyalkylene glycol di(meth)acrylate, tricyclodecanol di(meth)acrylate, di(meth)acrylate having a bisphenol A structure, and di(meth)acrylate having a hydrogenated bisphenol A structure.

[0078] The polyalkylene glycol di(meth)acrylate may be a compound represented by the following general formula (II): [ka] (In the formula, R 1 are each independently a hydrogen atom or a methyl group, and X 1 O and Y 1 Each O is independently an oxyalkylene group having 2 to 4 carbon atoms, m1, m2, and n1 are independently an integer of 0 to 40, m1+m2 is 1 to 40, and n1 is 0 to 20. Examples of the compound include compounds represented by the following formula:

[0079] The di(meth)acrylate having a bisphenol A structure includes a di(meth)acrylate represented by the following general formula (III): [ka] (In the formula, R 2 are each independently a hydrogen atom or a methyl group, and X 2 O and Y 2Each O is independently an oxyethylene group or an oxypropylene group, m3, m4, n2, and n3 are independently an integer of 0 to 40, m3+m4 is 1 to 40, and n2+n3 is 0 to 20. and the like. The number of structural units of oxyethylene groups or oxypropylene groups is an integer value in a single molecule, and is a rational number that is an average value in an aggregate of a plurality of molecules.

[0080] Examples of di(meth)acrylates having a hydrogenated bisphenol A structure include compounds in which hydrogen is added to the aromatic ring of the compound represented by the above formula (III).

[0081] The compound represented by the above formula (II) includes, in the formula, 1 = methyl group, m1 + m2 = 6 (average value), n1 = 12 (average value), X 1 O = oxyethylene group, and Y 1 Examples include a compound in which O=oxypropylene group (manufactured by Resonac, product name "FA-024M").

[0082] The compound represented by the formula (III) includes BPE-200 (wherein R 2 = methyl group, X 2 O = oxyethylene group, m3 + m4 = 4, and n2 = n3 = 0), BPE-500 (where R 2 = methyl group, X 2 O = oxyethylene group, m3 + m4 = 10, and n2 = n3 = 0), BPE-900 (where R 2 = methyl group, X 2 O = oxyethylene group, m3 + m4 = 17, and n2 = n3 = 0) (all manufactured by Shin-Nakamura Chemical Co., Ltd., product names), FA-321M (wherein R 2 = methyl group, X 2 O = oxyethylene group, m3 + m4 = 10, and n2 = n3 = 0), FA-P321M (wherein R 2 = methyl group, X 2O = oxypropylene group, m3 + m4 = 10, and n2 = n3 = 0) (all manufactured by Resonac Co., Ltd., product names), FA-P323M (wherein R 2 = methyl group, X 2 Examples include O = oxypropylene group, m3 + m4 = 30, and n2 = n3 = 2) (all manufactured by Resonac, product names).

[0083] From the viewpoint of excellent resolution, the component (B) preferably contains, as a bifunctional (meth)acrylate compound, a di(meth)acrylate having a bisphenol A structure and / or a di(meth)acrylate having a hydrogenated bisphenol A structure. The compound is contained in an amount of preferably 20% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, and particularly preferably 70% by mass or more, based on the total amount of the component (B). The compound is preferably contained in an amount of 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and particularly preferably 25% by mass or more, based on the total solid content of the photosensitive resin composition.

[0084] Commercially available bifunctional (meth)acrylate compounds include, for example, NK Ester (registered trademark) A-HD-N, A-NOD-N, A-DOD-N, A-NPG, 701A, A-200, A-400, A-600, A-1000, APG-200, APG-400, APG-700, A-PTMG65, A-DCP, ABE-300, A-BPE-4, A-BPE-10, A-BPE-20, HD-N, NOD-N, DOD-N, NPG, 701, 2G, 3G, 4G, 9G, and 14. G, 23G, 9PG, DCP, BPE-80N, BPE-100, BPE-200, BPE-500, BPE-900, BPE-1300N, NK Oligo (registered trademark) UA-4200, UA-160™, UA-290™, UA-W2A, UA-4400, UA-122P, U-200PA (all manufactured by Shin-Nakamura Chemical Co., Ltd.), Light Acrylate (registered trademark) 3EG-A, 4EG-A, 9EG-A, 14EG-A, PTMGA-250, NP-A, MPD-A, 1.6HX-A, and 1.9ND-A, DCP-A, BP-4EAL, BP-4PA, HPP-A, Light Ester G-201P (all manufactured by Kyoeisha Chemical Co., Ltd.), Fancryl (registered trademark) FA-124AS, FA-023M, FA-121M, FA-124M, FA-125M, FA-129AS, FA-137M, FA-220M, FA-222A, and FA-240 A, FA-240M, FA-320M, FA-3218M, FA-321A, FA-321M, FA-324A, FA-731A, FA-P240A, FA-P270A, FA-PTG9A, FA-PTG9M, FA-PTG28A, FA-PTG49A (all manufactured by Resonac), DPGDA, HDDA, TPGDA, EBECRYL 145, EBECRYL 150, PEG400DA, EBECRYL 11, IRR 214-K, EBECRYL 130, EBECRYL PEG200DMA (all manufactured by Daicel-Allnex Co., Ltd.), SR212, SR213, SR230, SR238F, SR259, SR268, SR272, SR306H, SR344, SR349, SR508, CD560, CD561, CD564, SR601, SR602, SR610, SR833S, SR9003, SR9045, SR9209, SR205, SR206, SR209, SR210, SR214, SR231, SR239, SR248, SR252, SR297, SR348, SR480, CD540, CD541, CD542, SR603, SR644, SR9036 (all manufactured by Arkema), KAYARAD (registered trademark) Examples include NPGDA, PEG400DA, FM-400, R-167, HX-220, HX-620, R-551, R-712, R-604, and R-684 (all manufactured by Nippon Kayaku Co., Ltd.).

[0085] Examples of trifunctional or higher (meth)acrylate compounds include trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, diglycerin (tetra)(meth)acrylate, ditrimethylolpropane (tetra / penta / hexa)(meth)acrylate, triglycerin (penta)(meth)acrylate, and dipentaerythritol (tetra / penta / hexa)(meth)acrylate.

[0086] The tri- or higher functional (meth)acrylate compound may be a compound obtained by forming a (meth)acrylate from (meth)acrylic acid and an alcohol having, as a central skeleton, three or more groups to which alkylene oxide groups can be added within the molecule, and having alkylene oxide groups (e.g., ethylene oxide group, propylene oxide group, and butylene oxide group) added thereto. Examples of such compounds include alkylene oxide-modified tri(meth)acrylate of trimethylolpropane, alkylene oxide-modified tri(meth)acrylate of glycerin, alkylene oxide-modified isocyanuric acid tri(meth)acrylate, alkylene oxide-modified pentaerythritol (tri / tetra)(meth)acrylate, alkylene oxide-modified tetra(meth)acrylate of diglycerin, alkylene oxide-modified ditrimethylolpropane (tetra / penta / hexa)(meth)acrylate, alkylene oxide-modified penta(meth)acrylate of triglycerin, and alkylene oxide-modified dipentaerythritol (tetra / penta / hexa)(meth)acrylate.

[0087] From the viewpoint of excellent developability, the tri- or higher functional (meth)acrylate compound preferably contains alkylene oxide-modified pentaerythritol (tri / tetra)(meth)acrylate and / or alkylene oxide-modified dipentaerythritol (tri / tetra)(meth)acrylate.

[0088] Commercially available tri- or higher functional (meth)acrylate compounds include, for example, NK Ester (registered trademark) A-TMPT, A-TMPT-9EO, AT-20E, A-GLY-3E, A-GLY-9E, A-GLY-20E, A-9300, A-9200YN, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMMT, ATM-35E, AD-TMP, A-DPH, and A-9550. , A-DPH-12E, TPOA-50, NK Oligo (registered trademark) UA-7100, UA-1100H, U-6LPA, UA-33H, U-10HA, U-10PA, U-15HA (all manufactured by Shin-Nakamura Chemical Co., Ltd.), Light Acrylate (registered trademark) TMP-A, cPE-3A, PE-4A, DPE-6A (all manufactured by Kyoeisha Chemical Co., Ltd.), FA-731A (all manufactured by Resonac Co., Ltd.), TMPTA, EBECRYL 160S, OTA 480, PETIA, PETRA, EBECRYL 40, PETA, EBECRYL 140, EBECRYL 1140, EBECRYL 1142, DPHA, EBECRYL 895, EBECRYL 896, EBECRYL TMPTMA (all manufactured by Daicel-Allnex Co., Ltd.), SR351S, SR368, SR415, SR444, SR454, SR492, SR499, CD501, SR502, SR9020, D9021, SR9035, SR295, SR355, SR399, SR494, SR9041 (all manufactured by Arkema), KAYARAD (registered trademark) Examples include GPO-303, TMPTA, THE-330, TPA-330, PET-30, T-1420(T), RP-1040, DPHA, DPEA-12, D-310, and DPCA-20 (all manufactured by Nippon Kayaku Co., Ltd.).

[0089] The component (B) may contain a hindered amine compound, which makes it less likely that residue will be left behind after the resist pattern is stripped. Examples of the hindered amine compound include those represented by the following general formula (IV): [ka] (In the formula, each R1 independently represents an alkyl group having one or more carbon atoms, and R2 independently represents hydrogen or an alkyl group having one or more carbon atoms, and the number of carbon atoms in R1 and R2 independently is 10 or less.) Examples of the compound represented by general formula (IV) include 1,2,2,6,6-pentamethylpiperidyl methacrylate.

[0090] The content of the hindered amine compound may be 1 mass % or more, 3 mass % or more, or 5 mass % or more, based on the total solid content of the photosensitive resin composition, and may be 20 mass % or less, 15 mass % or less, 10 mass % or less, or 0 mass %.

[0091] The hindered amine compound may correspond to a compound having one ethylenically unsaturated bond. The content of the compound having one ethylenically unsaturated bond (excluding the hindered amine compound when the hindered amine compound corresponds to a compound having one ethylenically unsaturated bond) may be 20% by mass or less, 10% by mass or less, 5% by mass or less, or 0% by mass based on the total solid content of the photosensitive resin composition.

[0092] In light of the above, specific examples of the component (B) that can be used in this embodiment are as follows: However, the component (B) that can be used in this embodiment is not limited to only the specific examples below. Dimethacrylate of polyethylene glycol with an average of X ethylene oxide units attached to each end of bisphenol A (for example, an average of 1 unit on each end, or an average of 5 units on each end) Tetramethacrylate with an average of 9 ethylene oxide units added to pentaerythritol Hexamethacrylate of polyethylene glycol, in which 13 ethylene oxide units are added to dipentaerythritol Dimethacrylate of polytetramethylene glycol (average of 28 repeating tetramethylene glycol units) Dimethacrylate of polypropylene glycol (average of 12 repeating propylene glycol units) Dimethacrylate of polypropylene glycol (average of 12 repeating propylene glycol units) Dimethacrylate of polyethylene glycol with an average of five ethylene oxide units attached to each end of hydrogenated bisphenol A

[0093] The content of component (B) is preferably 10 to 50% by mass based on the total solid content of the photosensitive resin composition. From the viewpoints of preventing poor curing of the photosensitive resin layer and suppressing delays in development time, the content is preferably 10% by mass or more. Furthermore, from the viewpoint of improving the developability of the resist pattern, the content is preferably 50% by mass or less. From the same viewpoints, the content is more preferably 20 to 45% by mass, and even more preferably 25 to 40% by mass.

[0094] The total content of components (A) and (B) is preferably 85% by mass or more, and more preferably 90% by mass or more, based on the total solid content of the photosensitive resin composition. By ensuring that the content is within the above range, the effects of the present invention, which are likely to be achieved by components (A) and (B), can be more effectively achieved. The total content of components (A) and (B) may be 99% by mass or less, or 95% by mass or less.

[0095] <Ratio of the content of component (A) to the content of component (B)> In this embodiment, the ratio of the content of the component (A) to the content of the component (B) in the photosensitive resin composition {content of the component (A) / content of the component (B)} is 1.40 or more and 2.00 or less. When the ratio is 1.40 or more, i.e., the amount of component (A) is sufficient relative to component (B), it is easy to enjoy the effects of component (A) and, by extension, copolymer (A-1).When the ratio is 2.00 or less, i.e., the amount of component (A) is not excessive relative to component (B), it is easy to ensure crosslinking efficiency in the exposure step.

[0096] <(C) component> Component (C) is a polymerization initiator. Component (C) is preferably a photopolymerization initiator that generates radicals when exposed to actinic rays, thereby initiating polymerization of component (B). Component (C) preferably contains a compound having a biimidazole structure.

[0097] Examples of the component (C) include hexaarylbiimidazole compounds, N-aryl-α-amino acid compounds, quinone compounds, aromatic ketone compounds, acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, benzoin ether compounds, dialkyl ketal compounds, thioxanthone compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, acridine compounds, and halogen compounds.

[0098] Examples of the hexaarylbiimidazole compound include a dimer of a compound having a lophine structure (lophine dimer), i.e., a dimer of 2,4,5-triarylimidazole, and 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole. Examples of lophine dimers include dimers of 2-(o-chlorophenyl)-4,5-diphenylimidazole (also known as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole), 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, and 2,2'-bis-( 2,4-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,6-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazo 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole bis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, and 2,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole.

[0099] From the viewpoint of high sensitivity, resolution, and adhesion, component (C) preferably contains a lophine dimer, more preferably 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-bis-(m-methoxyphenyl)imidazole dimer, or 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, and even more preferably 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer.

[0100] Examples of quinone compounds include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone.

[0101] Examples of aromatic ketone compounds include benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], and 4-methoxy-4'-dimethylaminobenzophenone. Aromatic ketone compounds function as photopolymerization initiators when used alone, but may also function as sensitizers when used in combination with other photopolymerization initiators.

[0102] Examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl ketone, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1. Examples of commercially available acetophenone compounds include the Irgacure series (manufactured by BASF: Irgacure-907, Irgacure-369, and Irgacure-379, etc.).

[0103] Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide. Commercially available acylphosphine oxide compounds include Lucirin TPO (both manufactured by BASF) and Irgacure-819 (both manufactured by BASF).

[0104] Examples of benzoin compounds and benzoin ether compounds include benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, and ethylbenzoin. Examples of dialkyl ketal compounds include benzyl dimethyl ketal and benzyl diethyl ketal. Examples of thioxanthone compounds include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone. Examples of dialkylaminobenzoate compounds include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, and 2-ethylhexyl-4-(dimethylamino)benzoate.

[0105] Examples of oxime ester compounds include 1-phenyl-1,2-propanedione-2-O-benzoyloxime and 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime. Commercially available oxime ester compounds include CGI-325, Irgacure-OXE01, and Irgacure-OXE02 (all manufactured by BASF). Examples of the acridine compound include 1,7-bis(9,9'-acridinyl)heptane and 9-phenylacridine. Examples of halogen compounds include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenylsulfone, carbon tetrabromide, tris(2,3-dibromopropyl)phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, chlorinated triazine compounds, and diaryliodonium compounds.

[0106] The content of component (C) is preferably 0.01 to 20 mass%, more preferably 0.5 to 10 mass%, based on the total solids content of the photosensitive resin composition. When the photosensitive resin composition contains a lophine dimer as component (C), the content of the lophine dimer is preferably 3.0 to 10 mass%, more preferably 4.0 to 9.0 mass%, and even more preferably 5.0 to 8.0 mass%, based on the total solids content of the photosensitive resin composition. By adjusting the content of component (C) within the above range, sufficient sensitivity can be easily obtained, making it easier to achieve high resolution.

[0107] <Component (D): Sensitizer> From the viewpoint of excellent sensitivity and resolution, the photosensitive resin composition preferably further contains a sensitizer (D). Component (D) accelerates the photopolymerization reaction by transferring the energy obtained by absorbing light to the initiator.

[0108] Examples of component (D) include pyrazoline derivatives, anthracene derivatives, naphthalene derivatives, oxazole derivatives, N-aryl-α-amino acid derivatives, and aromatic ketone derivatives substituted with an alkylamino group, etc. Among these, component (D) preferably includes a pyrazoline derivative or an anthracene derivative.

[0109] Examples of pyrazoline derivatives include 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-(4-(benzoxazol-2-yl)phenyl)-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline, 1-phenyl-3-(4-isopropylstyryl)-5-(4-isopropylphenyl)-pyrazoline, 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline, 1-phenyl-3-(3,5-dimethoxystyryl)-5-(3,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(3,4-dimethoxystyryl)-5-(3,4-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,6-dimethoxystyryl)-5-(2,6-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,5-dimethoxystyryl)-5-(2,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,3-dimethoxystyryl)-5-(2,3-dimethoxyphenyl)-pyrazoline, and 1-phenyl-3-(2,4-dimethoxystyryl)-5-(2,4-dimethoxyphenyl)-pyrazoline. Of these, the pyrazoline derivative is preferably 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline.

[0110] Examples of the anthracene derivatives include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-dipentoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, 2-ethyl-9,10-dibutoxyanthracene, 9-bromo-10-phenylanthracene, 9-chloro ... Examples of the anthracene derivative include bromo-10-phenylanthracene, 9-bromo-10-(2-naphthyl)anthracene, 9-bromo-10-(1-naphthyl)anthracene, 9-(2-biphenylyl)-10-bromoanthracene, 9-(4-biphenylyl)-10-bromoanthracene, 9-bromo-10-(9-phenanthryl)anthracene, 2-bromoanthracene, 9-bromoanthracene, 2-chloroanthracene, 9,10-dibromoanthracene, and 9-(3-bromophenyl)-10-phenylanthracene. Among these, 9,10-dibutoxyanthracene and 9,10-diphenylanthracene are preferred as the anthracene derivative.

[0111] Examples of naphthalene derivatives include 1-methoxynaphthalene, 1-ethoxynaphthalene, 1-propoxynaphthalene, 1-butoxynaphthalene, 1,4-dimethoxynaphthalene, 1-ethoxy-4-methoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-bis(n-butoxy)naphthalene, 1,4-bis(i-butoxy)naphthalene, 1,4-bis(n-pentyloxy)naphthalene, 1,4-bis(n-hexyloxy)naphthalene, and 1,4-bis(n-heptyloxy)naphthalene. Examples of the naphthalene derivative include 1,4-dibenzyloxynaphthalene, 1,4-diphenethyloxynaphthalene, 1,4-diglycidyloxynaphthalene, 1,4-bis(2-methylglycidyloxy)naphthalene, 1-naphthol, 2-naphthol, 1-(2-hydroxyethoxy)naphthalene, and 2-(2-hydroxyethoxy)naphthalene. Of these, 1,4-diethoxynaphthalene is preferred as the naphthalene derivative.

[0112] Examples of oxazole derivatives include 5-tert-butyl-2-[5-(5-tert-butyl-1,3-benzoxazol-2-yl)thiophen-2-yl]-1,3-benzoxazole and 2-[4-(1,3-benzoxazol-2-yl)naphthalen-1-yl]-1,3-benzoxazole.

[0113] Examples of the N-aryl-α-amino acid derivatives include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, N-(n-propyl)-N-phenylglycine, N-(n-butyl)-N-phenylglycine, N-(2-methoxyethyl)-N-phenylglycine, N-methyl-N-phenylalanine, N-ethyl-N-phenylalanine, N-(n-propyl)-N-phenylalanine, N-(n-butyl)-N-phenylalanine, N-methyl-N-phenylvaline, N-methyl-N-phenylleucine, N-methyl-N-(p-tolyl)glycine, N-ethyl-N-(p-tolyl)glycine, N-(n-propyl Examples of such glycine include N-(p-tolyl)glycine, N-(n-butyl)-N-(p-tolyl)glycine, N-methyl-N-(p-chlorophenyl)glycine, N-ethyl-N-(p-chlorophenyl)glycine, N-(n-propyl)-N-(p-chlorophenyl)glycine, N-methyl-N-(p-bromophenyl)glycine, N-ethyl-N-(p-bromophenyl)glycine, N-(n-butyl)-N-(p-bromophenyl)glycine, N,N'-diphenylglycine, N-methyl-N-(p-iodophenyl)glycine, N-(p-bromophenyl)glycine, N-(p-chlorophenyl)glycine, and N-(o-chlorophenyl)glycine.

[0114] Examples of the aromatic ketone derivatives substituted with an alkylamino group include benzophenone derivatives. alkylbenzophenone compounds such as benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, and 4-methylbenzophenone; benzophenone compounds having a halogen atom, such as 2-chlorobenzophenone, 4-chlorobenzophenone, and 4-bromobenzophenone; benzophenone compounds substituted with a carboxy group or an alkoxycarbonyl group, such as 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenonetetracarboxylic acid or its tetramethyl ester; bis(dialkylamino)benzophenone compounds such as 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(dicyclohexylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(dihydroxyethylamino)benzophenone, preferably 4,4'-bis(dialkylamino)benzophenone compounds; 4-Methoxy-4'-dimethylaminobenzophenone, 4-methoxybenzophenone, 4,4'-dimethoxybenzophenone, etc.; Examples include:

[0115] In one embodiment, component (D) may contain a compound having the following skeleton, either in addition to or in addition to the above skeleton. Examples of the skeleton include at least one skeleton selected from the group consisting of pyrene, coumarin, triarylamine, oxazole, and chrysene. This is likely to be advantageous from the viewpoint of sensitivity.

[0116] In one embodiment, component (D) may contain a boron compound that has absorption at h-line and / or i-line. The boron compound that has absorption at h-line and / or i-line is at least one compound selected from the group consisting of pyrazoline derivatives, anthracene derivatives, oxazole derivatives, N-aryl-α-amino acid derivatives, and aromatic ketone derivatives substituted with an alkylamino group, and is preferably a compound represented by the following general formula: *-BH2 *-B(OH)2 *-B(OR 1 )2 *-B(OH)(OR 1 ) (In the formula, R 1 each independently represents a monovalent organic group, and * represents the bonding point to the various skeletons. The compound is a compound containing at least one boron moiety selected from the group consisting of: Examples of this type of compound include boronic acids having a pyrazoline skeleton, an anthracene skeleton, and an oxazole skeleton. Among these, boronic acids having a 10-phenyl-9-anthracene skeleton (10-phenyl-9-anthraceneboronic acid) are preferred.

[0117] In the above boron compounds that have absorption for h-lines and / or i-lines, the definitions of "h-lines," "i-lines," and "having absorption" are the same as those in the [embodiment of the "first invention"].

[0118] The content of component (D) is preferably 0.01 to 2.0 mass %, and more preferably 0.3 to 1.5 mass %, based on the total mass of component (A).

[0119] <(E) Ingredient: Other ingredients> The photosensitive resin composition may optionally contain components other than the above components (A) to (D) {component (E): other components}. Examples of component (E) include colorants, leuco dyes, base dyes (dyes other than leuco dyes), antioxidants, and stabilizers.

[0120] (coloring agent) Examples of colorants include fuchsin, phthalocyanine green, auramine base, paramagenta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (e.g., EIZEN (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.), basic blue 20, diamond green (e.g., EIZEN (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.), 1,4-bis(4-methylphenylamino)-9,10-anthraquinone (e.g., OPLAS GREEN 533 manufactured by Orient Chemical Industry Co., Ltd.), 1,4-bis(butylamino)anthraquinone (e.g., OIL BLUE 2N manufactured by Orient Chemical Industry Co., Ltd.), and 1,4-bis(isopropylamino)-9,10-anthraquinone (e.g., OIL BLUE 630 manufactured by Orient Chemical Industry Co., Ltd.).

[0121] The content of the colorant is preferably 0.01 to 10 mass %, more preferably 0.1 to 5 mass %, and even more preferably 0.5 to 2 mass %, based on the total solid content of the photosensitive resin composition.

[0122] (leuco dye) Leuco dyes include, for example, leuco crystal violet (tris[4-(dimethylamino)phenyl]methane) and 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide.

[0123] The content of the leuco dye is preferably 0.01 to 2 mass %, more preferably 0.1 to 1.5 mass %, based on the total solid content of the photosensitive resin composition.

[0124] (base dye) Examples of base dyes (dyes other than leuco dyes) include Basic Green 1 [CAS number (hereinafter the same): 633-03-4] (e.g., Aizen Diamond Green GH, trade name, manufactured by Hodogaya Chemical Co., Ltd.), Fuchsin [632-99-5], Methyl Violet [603-47-4], Methyl Green [82-94-0], Victoria Blue B [2580-56-5], Basic Blue 7 [2390-60-5] (e.g., Aizen Victoria Pure Blue BOH, trade name, manufactured by Hodogaya Chemical Co., Ltd.), Rhodamine B [81-88-9], Rhodamine 6G [989-38-8], and Basic Yellow 2 [2465-27-2].

[0125] The content of the base dye is preferably 0.001 to 3 mass %, more preferably 0.01 to 2 mass %, and even more preferably 0.04 to 1 mass %, based on the total solid content of the photosensitive resin composition.

[0126] (antioxidant) Examples of antioxidants include triphenyl phosphite (e.g., manufactured by Asahi Denka Kogyo Co., Ltd., trade name: TPP), tris(2,4-di-tert-butylphenyl) phosphite (e.g., manufactured by ADEKA Corporation, trade name: 2112), tris(mononylphenyl) phosphite (e.g., manufactured by ADEKA Corporation, trade name: 1178), and bis(mononylphenyl)-dinonylphenyl phosphite (e.g., manufactured by Asahi Denka Kogyo Co., Ltd., trade name: 329K).

[0127] The content of the antioxidant is preferably 0.01 to 0.8 mass %, more preferably 0.01 to 0.3 mass %, based on the total mass of the photosensitive resin composition.

[0128] (stabilizer) Examples of the stabilizer include at least one of a radical polymerization inhibitor and an alkylene oxide compound having a glycidyl group.

[0129] Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], nitrosophenylhydroxylamine aluminum salt (for example, aluminum salt with 3 moles of nitrosophenylhydroxylamine added), diphenyl ether, Examples of the radical polymerization inhibitor include phenylnitrosamine, hydroquinone, N-nitrosodiphenylamine, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt. Among these, preferred radical polymerization inhibitors are p-methoxyphenol, tert-butylcatechol, 2,6-di-tert-butyl-p-cresol, phenothiazine, and triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate].

[0130] Examples of alkylene oxide compounds having a glycidyl group include neopentyl glycol diglycidyl ether (e.g., Epolite 1500NP manufactured by Kyoeisha Chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (e.g., Epolite 400E manufactured by Kyoeisha Chemical Co., Ltd.), bisphenol A-propylene oxide 2-mol adduct diglycidyl ether (e.g., Epolite 3002 manufactured by Kyoeisha Chemical Co., Ltd.), and 1,6-hexanediol diglycidyl ether (e.g., Epolite 1600 manufactured by Kyoeisha Chemical Co., Ltd.).

[0131] The total content of the radical polymerization inhibitor and the alkylene oxide compound having a glycidyl group is preferably 0.001 to 3 mass %, more preferably 0.05 to 1 mass %, based on the total solid content of the photosensitive resin composition.

[0132] (Other optional ingredients) Other components include carboxybenzotriazoles. The content of the carboxybenzotriazoles is, for example, 0.01 mass % or more and 5 mass % or less based on the total solid content of the photosensitive resin composition.

[0133] [Prepared liquid (coating liquid) for producing photosensitive resin composition] A preparation liquid for producing the photosensitive resin composition can be prepared by mixing the photosensitive resin composition with a solvent. ketones such as acetone and methyl ethyl ketone (MEK); Alcohols such as methanol, ethanol, and isopropyl alcohol; It is preferable to mix the photosensitive resin composition and the solvent so that the viscosity of the prepared solution at 25°C is 500 to 4000 mPa·sec.

[0134] [Second embodiment] The second embodiment of the present invention will be described below, focusing on the differences from the first embodiment. The photosensitive resin laminate of the second embodiment of the present invention is also included in the present invention. In the description of this embodiment, if there are elements that have already been mentioned in the first embodiment, the description of such elements in the first embodiment may be referred to.

[0135] In the photosensitive resin laminate of this embodiment, The following method: (1) After forming the photosensitive resin layer on a flexible substrate, the layer is exposed to light with an energy amount that leaves 15 steps on a Stouffer Industries 41-step step tablet, with a width of 1 inch and a length of 250 mm, to obtain a cured film on the substrate. (2) The exposed substrate is developed using a 1% by mass Na2CO3 aqueous solution at 30°C for twice the shortest development time. (3) After development, the substrate is washed with water for twice the minimum development time. (4) After washing with water, the substrate is cut into a 1.2 inch wide piece so that the 1 inch wide cured photosensitive resin layer is located in the center of the width direction, thereby obtaining a sample. (5) Cylindrical Mandrel Method A mandrel test in accordance with the method of JIS K5600-5-1 is carried out on the sample. (6) The smallest mandrel diameter at which cracks are not observed in the cured film, or the smallest mandrel diameter at which peeling of the cured film from the substrate is not observed, is determined. The minimum mandrel diameter, calculated by

[0136] The smallest mandrel diameter is preferably 6 mm or less, and may be 2 mm or more. The photosensitive resin laminate of this embodiment is excellent in the ability to form independent thin lines.

[0137] The photosensitive resin laminate of this embodiment has a support and a photosensitive resin layer containing a photosensitive resin composition. Here, as the photosensitive resin composition in this embodiment, for example, the photosensitive resin composition explained in the first embodiment can be used.

[0138] Further, the photosensitive resin composition in this embodiment is Ingredients: (A) Alkali-soluble polymer; (B) a compound having an ethylenically unsaturated bond; and (C) a polymerization initiator; Including, The copolymer (A-1) contains at least the following components: (a1) (meth)acrylic acid; (a2) styrene derivatives; and having a structural unit derived from The content of the (a2) component is 25% by mass or more. A photosensitive resin composition can also be used.

[0139] In this embodiment, the components (A) to (C) and the components (a1) to (a2) may be referred to the explanation in the first embodiment. For example, the description in the first embodiment above may also be referred to for the preferred proportion of the structural units derived from component (a2).

[0140] In this embodiment, a styrene derivative is used as one of the monomers in the copolymer (A-1), which tends to provide excellent adhesion. Furthermore, according to this embodiment, by including a large amount (e.g., 25% by mass or more) of the styrene derivative as component (a2) and by using it in combination with specific components other than component (a2), the composition can be improved in adhesion while providing flexibility to the cured film. In other words, a favorable balance can be achieved between adhesion and various properties (e.g., flexibility of the cured film), resulting in excellent independent fine wire formability.

[0141] The resist pattern is formed, for example, with a predetermined width (line; L) and interval (space; S). The ratio of the space to the line (i.e., the value of x when the line / space (L / S) is expressed as a ratio of "1:x") may be set appropriately. In this regard, if the value of x is relatively small, the proportion of the width L (line) in the L / S tends to be large, making it easier to ensure a sufficient contact area between the resist and the substrate. In this case, excellent adhesion between the substrate and the resist pattern tends to directly lead to excellent formability of the resist pattern.

[0142] On the other hand, as the value of x becomes relatively larger, the ratio of the interval S (space) in the L / S increases, and the resist pattern becomes finer than conventional patterns, and the properties of "independent thin lines" with wide gaps between the patterns become stronger. This type of independent thin lines is easily subjected to external forces during development to form the independent thin lines. Therefore, the resist pattern tends to be destroyed during development, making it difficult to form the independent thin lines.

[0143] In contrast to this, the present embodiment is based on the idea that this type of independent thin wire can be realized by satisfying a suitable balance between such adhesion and various properties (for example, flexibility of the cured film), on the premise that the independent thin wire has excellent adhesion between the substrate and the resist pattern.

[0144] As described above, in a resist pattern with L / S=1:x, the smaller x is, the greater the contribution of adhesion tends to be, while the larger x is, the greater the contribution of flexibility tends to be. In recent years, with the miniaturization and increasing density of electronic devices, there has been an increasing demand for independent thin wires with a large x, and this embodiment can fully meet such expectations.

[0145] The proportion of the structural units derived from component (a2) is preferably 10% by mass or more, more preferably 25% by mass or more, even more preferably 35% by mass or more, and particularly preferably 40% by mass or more, based on component (A). The proportion of the structural units derived from component (a2) may be 70% by mass or less, or may be 60% by mass or less, based on component (A). When the proportion of the structural units derived from component (a2) is within the above range, the effects of this embodiment are easily achieved.

[0146] The product of "the proportion of structural units derived from component (a2) based on component (A)" and "the proportion of component (A) in the photosensitive resin composition" is preferably 6% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and particularly preferably 20% by mass or more. This product may be 45% by mass or less. When this product is within the above range, the effects of this embodiment are easily obtained.

[0147] <An example of a means for achieving both good adhesion and good flexibility of the cured film> An example of a means for achieving both good adhesion and good flexibility of the cured film will be described below. 1. Adopting an (A) component that is advantageous for good flexibility and increasing the (A) / (B) value 1-1 One example of a method for achieving both good adhesion and good flexibility of the cured film is to use component (A), which is advantageous for good flexibility, and increase the value of (A) / (B). When component (A) contains copolymer (A-1) with a high proportion of components (a2) and (a3), it is easy to achieve both good adhesion and good flexibility, and an excellent balance between the two is also easily achieved. 1-2 In the above "Part 1", the copolymer (A-1) may contain the component (a4), which is further advantageous for good flexibility. The glass transition temperature Tg of the homopolymer of the component (a4) i However, the glass transition temperature Tg of the homopolymer of component (a2) and component (a3) i When the glass transition temperature Tg of the copolymer (A-1) is lower than that of the copolymer (A-2), the use of such component (a4) makes it easy to adjust the glass transition temperature Tg of the copolymer (A-1) lower, which is likely to be advantageous from the viewpoint of realizing both good adhesion and good flexibility, and from the viewpoint of achieving an excellent balance between the two. Furthermore, since the component (A) contains a copolymer (A-1) in which the components (a2) and (a3) ​​account for a high proportion, it is possible to avoid the inclusion of a large amount of the component (a1) having a carboxyl group, which is likely to be advantageous from the viewpoint of flexibility of the cured film.

[0148] 1-3 In the above "1-1" or "1-2," the composition may contain a (B) component, which is further advantageous for achieving good adhesion. Examples of such a (B) component include alkylene oxide-modified bifunctional monomers. Examples of this type of monomer include compounds represented by the above general formula (III).

[0149] With regard to the above <<1. Means for employing component (A) advantageous for good flexibility and increasing the value of (A) / (B)>>, the contents of the first embodiment may be referred to.

[0150] 2. Means for increasing the content of component (B), which is advantageous for good flexibility 2-1 One example of a means for achieving both good adhesion and good flexibility of the cured film is to increase the content of component (B), which is advantageous for good flexibility. The ratio of the content of component (A) to the content of component (B) in the photosensitive resin composition (content of component (A) / content of component (B)) may be appropriately adjusted so that the content of component (B) is higher. When this ratio is 1.0 or more and 1.4 or less, the content of component (B) is extremely high relative to the content of component (A).

[0151] 2-2 A compound with a flexible skeleton may be used as component (B). Examples of the "compound with a flexible skeleton" include polyfunctional (trifunctional or higher) compounds that do not have a quaternary carbon atom, among the various compounds exemplified as component (B). Furthermore, with regard to the "compound having a flexible skeleton" referred to here, for example, when it contains a compound represented by the above general formula (II) or the above general formula (III), the flexibility tends to increase as the number of repeating units (alkylene oxide chains) increases.

[0152] <Various configurations> <Configuration based on minimum development time> In this embodiment, the shortest development time when a 1 mass % Na2CO3 aqueous solution at 30°C is sprayed onto the photosensitive resin layer for a predetermined time is preferably 0.6 to 1.1 seconds per 1 μm of film thickness. If the development time is too long, a long development time is required to form the resist pattern, in which case the resist pattern is likely to be destroyed. On the other hand, if the development time is too short, development proceeds too rapidly, making the resist pattern susceptible to external forces during the formation of the resist pattern, in which case the resist pattern is likely to be destroyed.

[0153] ·Means to control development time One method for controlling the development time is to adjust the acid equivalent of component (A). That is, one method is to adjust the amount of component (a1) in component (A) so that the acid equivalent of component (A) is 100 to 600. Other means for controlling the development time include, for example, the following means (1) to (4). Among these, the following means (1) and (2) are advantageous for shortening the development time.

[0154] (1) Controlling the type and content of the monomer in component (A). For example, if a highly hydrophilic monomer (other than component (a1)) is selected as the monomer in component (A), or if the content of such a monomer is high, it is easy to control the development time to be shorter. Examples of such monomers include hydroxyethyl (meth)acrylate (HEMA) and glycerin mono(meth)acrylate.

[0155] (2) The type and content of component (B) are controlled. For example, component (B) may be: A compound represented by the general formula (II) or the general formula (III) having a large number of repeating units (alkylene oxide chains); and / or Polyfunctional (e.g., trifunctional or more) compounds; When the content of these is large, the development time can be easily shortened.

[0156] In particular, in the composition according to the above-mentioned "1. Means of using component (A), which is advantageous for good flexibility, and increasing the value of (A) / (B)," the content of component (A) is high, and in this case, the development time is likely to be slow. Here, when the means of lowering Tg described in the above "1-2" (i.e., including component (a4) and avoiding the inclusion of a large amount of component (a1) having a carboxyl group) is adopted to impart flexibility, the hydrophobicity of component (A) is likely to increase, and as a result, the development time is likely to be slow. Therefore, in the composition according to the above <<1. Means of employing component (A) advantageous for good flexibility and increasing the value of (A) / (B)>>, it is particularly preferable to utilize the above means (1) to (2) and adjust the shortest development time to 0.6 to 1.1 times the film thickness.

[0157] Advantageous means for preventing the development time from being shortened too much include the following means (3) and (4). The term "not shortening too much" used here means, for example, but is not limited to, a minimum development time of 0.6 seconds / μm or less.

[0158] (3) The type and content of the monomer in component (A) is controlled. For example, if a monomer with excellent hydrophobicity is selected as the monomer in component (A), or if the content of such a monomer is high, it is advantageous to prevent excessive shortening of the development time. Examples of such monomers include styrene derivatives, particularly styrene.

[0159] (4) Controlling the type and content of component (B). For example, when component (B) contains a highly hydrophobic compound, or when the content of such a compound is high, it is advantageous to prevent excessive shortening of the development time. Regardless of the type of component (B), reducing the content of component (B) in the composition (relatively increasing the content of component (A)) is also advantageous in preventing the development time from being shortened too much.

[0160] ≪(C)~(D) ingredients, etc.≫ In this embodiment, the contents of the first embodiment may be referred to for the components (C) to (D) and other components that may be optionally included.

[0161] <Film Thickness> The thickness of the photosensitive resin layer is preferably 10 to 50 μm. If the thickness of the photosensitive resin layer is within this range, it is easy to achieve the purpose of this embodiment, which is to improve the formability of independent thin lines.

[0162] [Elements that may be common to both the first and second embodiments] For convenience, elements that may be common to both the first embodiment and the second embodiment are collectively described below. However, the elements that may be common to both are not limited to the contents described below, and elements related to the contents described below may differ between the two. If there are differences between the content described below and the content described in the above [First Embodiment] or the content described in the above [Second Embodiment], either one may be adopted.

[0163] [Photosensitive Resin Laminate] The photosensitive resin laminate has, for example, a support and a photosensitive resin layer obtained from a photosensitive resin composition. The photosensitive resin laminate is preferably a dry film resist from the viewpoint of easily achieving the effects of the present invention. It can also be understood that the photosensitive resin composition is preferably used as a dry film resist.

[0164] <Support> The support is preferably a transparent film that transmits light emitted from an exposure light source. Examples of the support include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, and cellulose derivative film. These films may be stretched as needed. The support may be single-layered or multi-layered.

[0165] When the photosensitive resin layer is exposed through a support, the thickness of the support is related to the transmission distance of the exposure light source. Therefore, a thinner support is advantageous for image formation and also economically. On the other hand, taking into consideration the function of maintaining strength, the support thickness is preferably 5 to 50 μm, more preferably 10 to 30 μm. The haze of the support is preferably 5 or less.

[0166] <Photosensitive resin layer> The thickness of the photosensitive resin layer is preferably 3 to 100 μm, more preferably 10 to 50 μm, and even more preferably 15 to 50 μm. The thinner the photosensitive resin layer, the more easily the resolution improves, and the thicker the photosensitive resin layer, the more easily the film strength improves. Therefore, the thickness of the photosensitive resin layer can be appropriately selected depending on the field and use to which the photosensitive resin laminate is applied.

[0167] <Protective layer> The photosensitive resin laminate may have a protective layer on the side of the photosensitive resin layer opposite the support. Examples of the protective layer include a polyethylene film, a polypropylene film, a polyethylene terephthalate film, and a polyester film. These films may be stretched as necessary. The protective layer may be a single layer or multiple layers.

[0168] The protective layer has an appropriate adhesive strength. The adhesive strength of the protective layer to the photosensitive resin layer is preferably smaller than the adhesive strength of the support to the photosensitive resin layer, and the protective layer can be easily peeled off from the photosensitive resin laminate. From this viewpoint, the protective layer is preferably a polyethylene terephthalate (PET) film or a biaxially oriented polypropylene (OPP) film.

[0169] The thickness of the protective layer is preferably 10 to 100 μm, more preferably 10 to 50 μm. In particular, when the protective layer is a polyethylene terephthalate (PET) film or a biaxially oriented polypropylene (OPP) film, the thickness is preferably 5 to 100 μm, more preferably 8 to 50 μm, and even more preferably 10 to 30 μm.

[0170] The protective layer preferably has a release layer on its surface. This allows the protective film to be easily and conveniently peeled off from the photosensitive resin layer. Release layers are classified, for example, into silicone compounds and non-silicone compounds. The release layer may have an antistatic function, i.e., may be an antistatic layer. In this case, charging between the photosensitive resin layer and the protective film can be prevented, making it easier to peel the protective film from the photosensitive resin layer. In one embodiment, the protective layer is preferably a PET film having an antistatic function.

[0171] Examples of silicone compounds include: A condensation reaction type silicone resin obtained by reacting a polydimethylsiloxane having silanol groups at both ends with a polymethylhydrogensiloxane or a polymethylmethoxysiloxane; Addition reaction type silicone resin obtained by reacting dimethylsiloxane-methylvinylsiloxane copolymer or dimethylsiloxane-methylhexenylsiloxane copolymer with polymethylhydrogensiloxane; UV-curable or electron beam-curable silicone resins obtained by curing acrylic silicones, epoxy group-containing silicones, etc. with UV rays or electron beams; Modified silicone resins such as epoxy-modified silicone resins (silicone epoxy), polyester-modified silicone resins (silicone polyester), acrylic-modified silicone resins (silicone acrylic), phenol-modified silicone resins (silicone phenol), alkyd-modified silicone resins (silicone alkyd), and melamine-modified silicone resins (silicone melamine); Examples include:

[0172] Examples of non-silicone compounds include alkyd resins, long-chain alkyl resins, acrylic resins, and polyolefin resins.

[0173] The thickness of the release layer is preferably 0.001 to 2 μm, more preferably 0.005 to 1 μm, and even more preferably 0.01 to 0.5 μm. If the thickness is equal to or less than the upper limit, the appearance of the coating film after peeling off the protective layer is likely to be good, and the coating film is likely to be sufficiently cured. On the other hand, if the thickness is equal to or more than the lower limit, sufficient releasability is likely to be ensured.

[0174] [Method for producing photosensitive resin laminate] A photosensitive resin laminate can be produced by sequentially laminating a photosensitive resin layer and, if necessary, a protective layer on a support. An example of the production method is as follows. First, a prepared liquid (coating liquid) of the photosensitive resin composition is prepared as described above. Next, the prepared liquid is applied to the support using a bar coater or a roll coater and dried, thereby producing a photosensitive resin layer on the support. Thereafter, if necessary, a protective layer is laminated on the photosensitive resin layer, thereby producing a photosensitive resin laminate.

[0175] [Method for forming a resist pattern and method for forming a wiring pattern] Each of the present embodiments includes a method for forming a resist pattern using a photosensitive resin composition. Such a method comprises the following steps: a lamination step of laminating the photosensitive resin layer of the photosensitive resin laminate onto a substrate; A step of exposing the photosensitive resin layer of the laminated photosensitive resin laminate (exposure step), and a step of removing unexposed areas of the photosensitive resin layer (development step); It has.

[0176] Yet another aspect of the above embodiment is a method for forming a wiring pattern. Such a method comprises the following steps: The substrate on which the resist pattern has been formed by the above method is subjected to plating treatment if necessary, followed by an etching step (etching step), a peeling step The wiring pattern forming method includes the steps of:

[0177] An example of a method for forming a resist pattern and a wiring pattern will be described below. <Lamination process> Specifically, in the lamination step, after peeling off the protective film from the photosensitive resin laminate, the resist layer is thermocompressed onto the surface of the substrate using a laminator, and lamination is performed once or multiple times. Examples of substrate materials include copper, stainless steel (SUS), glass, and indium tin oxide (ITO), with a copper-clad laminate being preferred. If desired, the substrate may be cleaned with, for example, an aqueous H2SO4 solution with a concentration of approximately 10% by mass to prepare the substrate surface. The heating temperature during lamination is generally 40 to 160°C, and more preferably 80 to 120°C. Thermocompression bonding can be performed using a laminator equipped with rolls, or by repeatedly passing the laminate of the substrate and the photosensitive resin composition layer through the rolls several times. Thermocompression bonding can be performed under reduced pressure as desired. Thermocompression bonding can also be performed two or more times, which facilitates improving the adhesion of the resulting resist pattern to the substrate. When pressure bonding is performed two or more times, a two-stage laminator equipped with two rolls may be used, and the laminate of the substrate and the photosensitive resin layer may be passed repeatedly through the rolls.

[0178] <Exposure process> In the exposure step, the resist layer is exposed to an ultraviolet light source or the like using an exposure machine such as a contact aligner, mirror projection, or stepper, either directly or through a patterned photomask or reticle. The exposure step may be performed after peeling off the support film, as desired, or through the support film. When exposure is performed through a photomask, the exposure dose is determined by the illuminance of the light source and the exposure time, and may be measured using an actinometer. In the exposure step, direct imaging exposure may be performed. In direct imaging exposure, exposure is performed directly on the substrate using a drawing device without using a photomask. A semiconductor laser or an ultra-high pressure mercury lamp with a wavelength of 350 nm to 410 nm is used as the light source. When the drawing pattern is controlled by a computer, the exposure dose is determined by the illuminance of the exposure light source and the moving speed of the substrate.

[0179] The exposure method used in the exposure step is preferably at least one method selected from the group consisting of projection exposure, proximity exposure, contact exposure, direct imaging exposure, and electron beam direct writing, and more preferably projection exposure or direct imaging exposure.

[0180] <Heating process> A heating step may be performed between the exposure step and the development step. The heating temperature is preferably 30 to 200°C, more preferably 30 to 150°C, and even more preferably 35 to 120°C. By performing this heating step, it is possible to improve resolution and adhesion. For heating, a hot air, infrared, or far-infrared heating oven, a thermostatic oven, a hot plate, a hot air dryer, an infrared dryer, a hot roll, or the like can be used. The heating time is preferably 1 to 300 seconds, more preferably 5 to 120 seconds.

[0181] The time elapsed from the exposure step to the heating step, more precisely the time elapsed from the time exposure is stopped to the time heating is started, is preferably 10 to 600 seconds, more preferably 20 to 300 seconds.The time elapsed from the time heating is started to the time heating is stopped is preferably 1 to 120 seconds, more preferably 5 to 60 seconds.

[0182] <Developing process> In the development process, the unexposed portions of the exposed resist layer are removed with a developer using a developing device to form a resist pattern. If a support film is present on the resist layer after exposure, the support film is removed. Next, the unexposed portions are developed and removed using a developer consisting of an aqueous alkaline solution to obtain a resist pattern. As a development method for developing the exposed (irradiated) resist layer, any method can be selected from conventionally known photoresist development methods, such as the rotary spray method, the paddle method, and the immersion method accompanied by ultrasonic treatment.

[0183] The alkaline aqueous solution used as the developer is preferably an aqueous solution of Na2CO3, K2CO3, or tetramethylammonium hydroxide. The alkaline aqueous solution is selected according to the characteristics of the resist layer, but an aqueous Na2CO3 solution with a concentration of 0.2% by mass to 2% by mass is generally used. The alkaline aqueous solution may contain a surfactant, an antifoaming agent, a small amount of an organic solvent to promote development, etc. The temperature of the developer during the development step is preferably kept constant within the range of 20 to 40°C.

[0184] The development step preferably includes a water-washing step for removing the developer contained in the resist pattern after development. The wash water may be pure water, industrial water, or other water selected according to the characteristics of the resist layer. To improve the resolution and shape of the resist pattern, a polyvalent metal salt such as MgSO4 may be added at a concentration of 0.001 to 1% by mass. The temperature of the wash water in the water-washing step is preferably kept constant within the range of 20 to 40°C.

[0185] A resist pattern can be obtained by the above steps, but if desired, a heat treatment can be further carried out at 60 to 300°C for 1 to 120 minutes. By carrying out this heat treatment, the chemical resistance of the resist pattern can be improved. For the heat treatment, a heating furnace using hot air, infrared rays, or far infrared rays can be used.

[0186] To obtain a conductive pattern, a conductive pattern forming step may be carried out after the developing step or heating step, in which the substrate on which the resist pattern has been formed is etched or plated.

[0187] <Conductor pattern formation process> The conductive pattern forming step is a step of forming a conductive pattern by using a known etching method or plating method on the substrate surface (for example, copper surface) on which a resist pattern has been formed by development.

[0188] The method for forming the conductive pattern by plating is, for example, as follows. After the development step, the substrate is immersed in an acidic degreasing bath such as a 1 to 50 mass % aqueous sulfuric acid solution for 1 to 60 minutes at 20 to 60° C. After rinsing the immersed substrate with water, it is immersed in a 1 to 50 mass % aqueous sulfuric acid solution at room temperature for 1 to 60 minutes.

[0189] An aqueous solution containing 1 to 15% by mass of copper sulfate, 0.1 to 30% by mass of sulfuric acid, and 1 to 1,000 ppm of hydrochloric acid is prepared, followed by the addition of 0.01 to 40 ml / L and 1 to 200 ml / L of brighteners (in one embodiment, Cupracid HL and Cupracid GS manufactured by Atotech Corporation), respectively, to prepare a copper sulfate plating solution. The prepared copper sulfate plating solution is used for plating in a Haring Cell uniform plating apparatus (manufactured by Yamamoto Plating Tester Co., Ltd.) at an applied current of 0.01 to 10 A for 1 to 300 minutes to form a conductor pattern. The thickness of the copper plating film depends on the thickness of the resist pattern, but is preferably 1 μm or more and equal to the thickness of the resist pattern (μm) minus 2 μm or less. In this disclosure, the thickness of the resist pattern refers to the thickness of the resist layer.

[0190] Examples of methods for forming a conductive pattern by etching include flash etching. In flash etching, the copper seed layer can be removed using a specific etching solution. Examples of the etching solution include, but are not limited to, a mixed etching solution of sulfuric acid and hydrogen peroxide (manufactured by Ebara Densan Co., Ltd.).

[0191] [Conductor pattern manufacturing method] The method for producing a conductor pattern is carried out by, for example, using a metal plate or a metal-coated insulating plate as a substrate, forming a resist pattern by the above-mentioned resist pattern forming method, and then carrying out a conductor pattern forming step.

[0192] <Peeling process> Furthermore, after the conductive pattern is produced by the above-described method for producing a conductive pattern, a peeling step may be performed in which the resist pattern is peeled off from the substrate using an aqueous solution having a stronger alkalinity than the developer. By performing the peeling step, a wiring board (in one embodiment, a printed wiring board) having a desired wiring pattern can be obtained.

[0193] The aqueous alkaline solution used for stripping (hereinafter also referred to as "stripping solution") is not particularly limited, but an aqueous solution of NaOH or KOH with a concentration of 2% by mass to 20% by mass, or an organic amine-based stripping solution is generally used. A small amount of a water-soluble solvent may be added to the stripping solution. Examples of the water-soluble solvent include alcohol. The temperature of the stripping solution in the stripping step is preferably within the range of 40 to 70°C, and the immersion time in the stripping solution is preferably 1 to 60 minutes.

[0194] [Method for manufacturing a wiring board] In one aspect, a method for producing a wiring board using the photosensitive resin laminate according to the above embodiment includes the following steps: a lamination step in which a photosensitive resin layer is laminated onto a substrate; an exposure step of exposing the photosensitive resin layer to light; a developing step of developing and removing the unexposed portions of the photosensitive resin layer to form a resist pattern; A conductive pattern forming step of etching or plating the substrate on which the resist pattern has been formed to form a conductive pattern; and a stripping step of stripping the resist pattern from the substrate; Includes: The lamination step, exposure step, development step, conductor pattern formation step, and peeling step, which are included in the method for manufacturing a wiring board according to the above embodiment, are the same as those described above.

[0195] The photosensitive resin laminate in the above embodiment can be used in the manufacture of printed wiring boards; the manufacture of lead frames for mounting IC chips; precision processing of metal foils such as the manufacture of metal masks; the manufacture of packages such as ball grid arrays (BGAs) and chip size packages (CSPs); the manufacture of tape substrates such as chip-on-film (COFs) and tape automated bonding (TABs); the manufacture of semiconductor bumps; and the manufacture of partition walls of flat panel displays such as ITO electrodes, address electrodes, and electromagnetic wave shields. [Example]

[0196] Unless otherwise specified, the various parameters described above are measured in accordance with the measurement methods in the examples described below.

[0197] [Preparation of evaluation samples] <Synthesis of component (A)> The monomers (copolymerization components) and azobisisobutyronitrile shown in the table below were mixed in the amounts (unit: parts by mass) shown in the table below to prepare solution (a). 200 g of methyl ethyl ketone and 100 g of ethanol were placed in a flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel, and nitrogen gas inlet tube, and the mixture was stirred while blowing nitrogen gas into the flask, and the mixture in the flask was heated to 80°C. 300 g of solution (a) was added dropwise to the mixture in the flask at a constant rate over 4 hours, and the mixture was then stirred at 80°C for 2 hours.

[0198] Next, 0.5 parts by mass of azobisisobutyronitrile was dissolved in 50 parts by mass of a mixture of 30 parts by mass of methyl ethyl ketone and 20 parts by mass of ethanol to prepare solution (b). 50 g of solution (b) was added dropwise to the solution in the flask at a constant rate over 10 minutes, followed by stirring at 80°C for 3 hours. The solution in the flask was then heated to 90°C over 30 minutes and then maintained at 90°C for 2 hours. Stirring was then stopped, and the solution was cooled to room temperature (25°C). This yielded solutions of alkali-soluble polymers A1-1 to A1-6, A2-1 to A2-5, and A3-1 to A3-5. The glass transition temperatures (Tg) and weight-average molecular weights (Mw) of these alkali-soluble polymers are shown in the table below.

[0199] The weight average molecular weight was determined by gel permeation chromatography (GPC) and calculated using a calibration curve of standard polystyrene. The GPC conditions are shown below. (GPC conditions) Pump: JASCO PU-4580 Degasser: DG-2080-53 Column oven: CO-1560 Columns: 4 in total (Shodex): KF-807 x 1, KF-806M x 2, KF-802.5 x 1 Eluent: tetrahydrofuran Measurement temperature: 40℃ Flow rate: 1.00mL / min Detector: JASCO RI-1530

[0200] <Preparation of Photosensitive Resin Laminate> The components shown in the table below (the numbers for each component indicate the amount (parts by mass) of solids) were mixed with ethanol measured to achieve a solids concentration of 60% so that the amount of each component in solid form was as shown in the table below, to obtain a preparation for a photosensitive resin composition. A 16 μm-thick polyethylene terephthalate film (Toray Industries, Inc., QS71) was used as a support film, and the preparation was applied to its surface using a bar coater, followed by drying for 2.5 minutes in a dryer at 95°C. This formed a 25 μm-thick photosensitive resin layer on the support film. This produced a photosensitive resin laminate.

[0201] Next, a 19 μm thick polyethylene film (manufactured by Tamapoly Co., Ltd., product name "GF-818") was attached as a protective layer to the side of the photosensitive resin layer opposite the support film to obtain a laminate. Here, the laminate of the support film, photosensitive resin layer, and protective film was treated as a photosensitive resin laminate.

[0202] <Surface preparation of the board> The surface of a copper-clad laminate with a total thickness of 0.4 mm, laminated with 18 μm-thick rolled copper foil, was prepared. The surface was then washed with a 10% by mass H2SO4 aqueous solution and then with pure water. The washed copper-clad laminate was preheated to 50°C.

[0203] <Lamination> While peeling off the protective film from the photosensitive resin laminate, the laminate was laminated onto a copper-clad laminate preheated to 50°C using a hot roll laminator (AL-700, manufactured by Asahi Kasei Corporation) at a roll temperature of 105°C so that the photosensitive resin layer was in contact with the surface of the copper-clad laminate. This produced a substrate for evaluation. The air pressure during lamination was set to 0.35 MPa, and the lamination speed was set to 1.5 m / min.

[0204] <Exposure> Two hours after lamination, the evaluation substrate was directly exposed using a direct imaging (DI) exposure pattern using a direct imaging exposure machine (FDi-3 manufactured by Oak Manufacturing Co., Ltd.). The exposure was performed using a Stouffer Industries 41-step step tablet as a mask, with an exposure dose that resulted in a maximum remaining film step count of 15 steps upon development. The maximum remaining film step count upon development was confirmed visually.

[0205] <Heating> Two minutes after exposure, the evaluation substrate was heated for 30 seconds in a constant temperature incubator with a blower (manufactured by Yamato Scientific Co., Ltd., DKM600) set at 70°C.

[0206] <Developing> The support film was peeled off from the evaluation substrate. Then, using an alkaline developer (manufactured by Fuji Kiko Co., Ltd., a dry film developer), the photosensitive resin layer was developed by spraying a 1% by mass Na2CO3 aqueous solution at 30°C for a predetermined time. Then, the photosensitive resin layer was washed by spraying pure water for a predetermined time. This resulted in a resist pattern on the evaluation substrate.

[0207] [evaluation] <Developability> The shortest time required for the unexposed portions of the photosensitive resin layer to completely dissolve was defined as the "shortest development time," and the developability was evaluated by ranking this shortest development time as follows: If the shortest development time is short, it is easy to shorten the development time, and if good results are obtained in the <developability> evaluation, improvement in productivity during wiring board production can be expected. (Evaluation criteria) Excellent (E): The shortest development time is 19 seconds or less. Good (G): The shortest development time is more than 19 seconds and 26 seconds or less. Unacceptable (P): The minimum development time exceeds 26 seconds.

[0208] <Resolution> The resolution was evaluated using a drawing pattern (see Figure 1) with an L / S of x / x {x = 5, 8, and 10 μm} (unit: μm). That is, the substrate that had been subjected to the above-mentioned <surface preparation> and <lamination> was subjected to direct imaging exposure according to the drawing pattern. Then, the above-mentioned <heating> and <development> were carried out to form a resist pattern. In the <development>, the development and water washing were carried out for a time twice as long as the shortest development time.

[0209] FIG. 1 is a plan view showing an example of the configuration of a drawing pattern. In the drawing, in a patterned region 100, an exposed region is designated by the reference numeral 10, and an unexposed region (shaded region) is designated by the reference numeral 1. The unexposed region 1 has a predetermined width and extends in the X direction, and a plurality of such unexposed regions 1 are arranged at predetermined intervals in the width direction (Y direction). In this example, the unexposed region 1 is removed through the <development> step, so that by exposing the photosensitive resin layer based on the patterned pattern of FIG. 1, it is theoretically expected that a resist pattern having an L / S corresponding to the width of the unexposed region 1 (S: space) and the width of the exposed region 10 (L: line) will be formed.

[0210] The substrate on which the resist pattern was formed was observed under an optical microscope at a magnification of 200x and evaluated according to the following criteria: Residual resist may occur if the unexposed portions of the resist are not sufficiently removed in the above <development>. (Evaluation criteria) Yu(E): No collapse, breakage or defect was observed in the resist pattern obtained using a drawing pattern with L / S=5 μm / 5 μm, and no remaining resist was observed between the resist patterns. Good (G): No collapse, breakage, or defect was observed in the resist pattern obtained using a drawing pattern with L / S = 8 μm / 8 μm, and no remaining resist was observed between the resist patterns (excluding cases rated "Excellent (E)"). Possible (A): No collapse, breakage, or defect was observed in the resist pattern obtained using a drawing pattern with L / S = 10 μm / 10 μm, and no remaining resist was observed between the resist patterns (excluding cases rated "Excellent (E)" or "Good (G)"). Not possible (P): A resist pattern obtained using a drawing pattern with L / S=10 μm / 10 μm is found to have collapsed, broken, or missing, or residual resist is found between the resist patterns.

[0211] <Independent fine line formation> The formability of independent fine lines was evaluated using a drawing pattern (see Figure 2) with L / S = x / 200 {x = 5, 8, and 10 μm} (unit: μm). That is, the substrate that had been subjected to the above-mentioned "surface preparation" and "lamination" was exposed using the drawing pattern. Then, the above-mentioned "heating" and "development" were carried out to form a resist pattern. In the "development," the development and water washing were carried out for a time twice as long as the shortest development time.

[0212] FIG. 2 is a plan view showing an example of the configuration of a drawing pattern. In the drawing, in the writing area 100A, the exposed area is designated by the reference numeral 10, and the unexposed area (shaded area) is designated by the reference numeral 1. The exposed area 10 has a predetermined width and extends in the x direction, and a plurality of such exposed areas 10 are arranged in the width direction (y direction) at predetermined intervals. In this example, the unexposed area 1 is removed through the <development> step, and therefore, based on the writing pattern of FIG. 2, it is theoretically expected that a resist pattern having an L / S corresponding to the width of the exposed area 10 (L: line) and the width of the unexposed area 1 (S: space) will be formed.

[0213] The substrate on which the resist pattern was formed was observed under an optical microscope at a magnification of 100 times and evaluated according to the following criteria. (Evaluation criteria) Yu(E): No breaks or defects were observed in the resist pattern obtained using a drawing pattern with L / S=5 μm / 200 μm. Good (G): No breaks or defects are observed in the resist pattern obtained using a drawing pattern with L / S=8μm / 200μm (excluding cases rated "Excellent (E)"). Possible (A): No breaks or defects are observed in the resist pattern obtained using a drawing pattern with L / S=10μm / 200μm (excluding cases rated "Excellent (E)" or "Good (G)"). Not possible (P): Breaks or defects are observed in the resist pattern obtained using a drawing pattern with L / S=10 μm / 200 μm.

[0214] <Flexibility of cured film> The above-described lamination process was performed on a flexible substrate (Nikkan Industries NIKKAFLEX F-30VC1 25RC11(H)) cut to a size of 200 mm x 250 mm, and a photosensitive resin layer was then formed on the substrate. The substrate was then exposed to light at an energy level sufficient to leave 15 steps on a Stouffer Industries 41-step step tablet, with a width of 1 inch and a length of 250 mm. The substrate was then developed for twice the shortest development time according to the above-described development process and washed with water. A sample was then prepared by cutting the substrate to a width of 1.2 inches, with the 1-inch-wide cured photosensitive resin layer positioned in the widthwise center.

[0215] The prepared samples were subjected to a mandrel test (cylindrical mandrel method; a bending resistance test conforming to JIS K5600-5-1-1999). The smallest mandrel diameter at which no cracks or peeling from the substrate were observed in the cured film on the sample was then determined, and flexibility was evaluated using this diameter according to the following criteria. The smaller this value, the higher the flexibility. (Evaluation criteria) Yu(E): The minimum mandrel diameter for which no cracks or peeling from the substrate were observed in the cured film was 6 mm or less. Good (G): No cracks or peeling from the substrate were observed in the cured film, and the minimum mandrel diameter was 8 mm or less (except in the case of an "Excellent (E)" rating). Not possible (P): No cracks or peeling from the substrate were observed in the cured film, and the minimum mandrel diameter was 10 mm or more (excluding cases with an "Excellent (E)" or "Good (G)" rating).

[0216] Observations of "cracking" and "peeling from the substrate" were performed visually. Observations of cracks in the cured film corresponded to "cracking," and observations of peeling of the cured film from the substrate corresponded to "peeling from the substrate." Observations of "chips" in the cured film were treated as being included in "cracking."

[0217] [Table 2]

[0218] [Table 3]

[0219] [Table 4]

[0220] [Table 5]

[0221] [Table 6]

[0222] [Table 7]

[0223] [Table 8]

[0224] From the above table, it was confirmed that, according to the examples, by controlling each item described in the example table (the type of each component and its content), excellent results were obtained in the evaluation of "independent thin line formability." [Industrial Applicability]

[0225] The present invention can be utilized in fields relating to photosensitive resin compositions, photosensitive resin laminates, and methods for forming resist patterns. The photosensitive resin composition of the present invention can be used to form wiring on printed wiring boards, etc. By using the photosensitive resin composition of the present invention, the above-mentioned photosensitive resin laminate that can be used industrially can be suitably obtained. The method for forming a resist pattern of the present invention can be suitably used in a process for forming a wiring pattern. [Explanation of symbols]

[0226] 1: Unexposed area (unexposed part) 10: Exposure area (exposure part) 100,100A: Drawing area L: Line S: Space

Claims

1. Ingredients: (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated bond; and (C) a polymerization initiator; A photosensitive resin composition comprising: The component (A) contains a copolymer (A-1), The copolymer (A-1) contains at least the following components: (a1) (meth)acrylic acid; (a2) styrene derivatives; and (a3) a compound having an alcoholic hydroxy group and a (meth)acryloyl group; having a structural unit derived from the proportion of the structural units derived from the component (a2) and the structural units derived from the component (a3) ​​in the copolymer (A-1) is 50 to 80 mass %, The proportion of the structural units derived from the component (a2) in the copolymer (A-1) is greater than the proportion of the structural units derived from the component (a3) ​​in the copolymer (A-1), and In the photosensitive resin composition, the ratio of the content of the component (A) to the content of the component (B) {content of the component (A) / content of the component (B)} is 1.40 or more and 2.00 or less. Photosensitive resin composition.

2. 2. The photosensitive resin composition according to claim 1, wherein the proportion of structural units derived from the component (a2) in the copolymer (A-1) is 30 to 70% by mass.

3. 2. The photosensitive resin composition according to claim 1, wherein the proportion of structural units derived from the component (a1) in the copolymer (A-1) is 25% by mass or less.

4. The photosensitive resin composition according to claim 1, wherein the copolymer (A-1) contains a structural unit derived from methacrylic acid as the component (a1).

5. The photosensitive resin composition according to claim 1, wherein the proportion of structural units derived from methacrylic acid in the copolymer (A-1) is 15 to 25% by mass.

6. 2. The photosensitive resin composition according to claim 1, wherein the proportion of structural units derived from the component (a3) ​​in the copolymer (A-1) is 5% by mass or more.

7. In the copolymer (A-1), the proportion of structural units derived from the component (a1) is 15 to 25% by mass, The proportion of structural units derived from the component (a2) is 30 to 70 mass %, and 2. The photosensitive resin composition according to claim 1, wherein the proportion of structural units derived from the component (a3) ​​is 5 to 30% by mass.

8. The copolymer (A-1) further contains the following components: (a4) The following general formula (I): 【Chemistry 1】 (In the formula, R １ represents a hydrogen atom or a methyl group, R ２ represents an alkyl group having 3 or more carbon atoms. Alkyl (meth)acrylates represented by the formula: having a structural unit derived from 2. The photosensitive resin composition according to claim 1, wherein the proportion of structural units derived from the component (a4) in the copolymer (A-1) is 1% by mass to 15% by mass.

9. In the copolymer (A-1), the proportion of structural units derived from the component (a1) is 15 to 25% by mass, the proportion of structural units derived from the component (a2) is 30 to 70 mass %, The proportion of structural units derived from the component (a3) ​​is 5 to 30 mass %, and 9. The photosensitive resin composition according to claim 8, wherein the proportion of structural units derived from the component (a4) is 1 to 15% by mass.

10. The R ２ The photosensitive resin composition according to claim 8, wherein represents an alkyl group having 3 to 12 carbon atoms.

11. 9. The photosensitive resin composition according to claim 8, wherein the component (a4) comprises 2-ethylhexyl (meth)acrylate.

12. 2. The photosensitive resin composition according to claim 1, wherein the weight average molecular weight of the copolymer (A-1) is 30,000 or more and 50,000 or less.

13. The photosensitive resin composition according to claim 1, wherein the copolymer (A-1) is contained in an amount of 10 mass% or more based on the total solid content of the photosensitive resin composition.

14. The photosensitive resin composition according to claim 1, wherein the copolymer (A-1) is contained in an amount of 30 mass% or more based on the total solid content of the photosensitive resin composition.

15. 2. The photosensitive resin composition according to claim 1, wherein the component (B) contains a bifunctional (meth)acrylate compound in an amount of 20% by mass or more based on the total solid content of the photosensitive resin composition.

16. The photosensitive resin composition according to claim 15, wherein the bifunctional (meth)acrylate compound includes a di(meth)acrylate having a bisphenol A structure.

17. The photosensitive resin composition according to claim 16, wherein the di(meth)acrylate having a bisphenol A structure is contained in an amount of 20 mass% or more based on the total solid content of the photosensitive resin composition.

18. 2. The photosensitive resin composition according to claim 1, wherein the ratio of the content of the component (A) to the content of the component (B) in the photosensitive resin composition {content of component (A) / content of component (B)} is 1.50 or more.

19. 2. The photosensitive resin composition according to claim 1, wherein the ratio of the content of the component (A) to the content of the component (B) in the photosensitive resin composition {content of component (A) / content of component (B)} is 1.70 or less.

20. The photosensitive resin composition according to claim 1 , wherein the component (C) comprises a compound having a biimidazole structure.

21. The photosensitive resin composition further contains a sensitizer, 2. The photosensitive resin composition according to claim 1, wherein the sensitizer comprises a compound having at least one skeleton selected from the group consisting of skeletons derived from pyrazoline derivatives, anthracene derivatives, naphthalene derivatives, and oxazole derivatives.

22. The photosensitive resin composition according to claim 21 , wherein the sensitizer comprises a compound having a skeleton derived from an anthracene derivative.

23. 22. The photosensitive resin composition according to claim 21, wherein the sensitizer comprises at least one compound selected from the group consisting of 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, and 10-phenyl-9-anthraceneboronic acid.

24. A photosensitive resin laminate comprising a support and a photosensitive resin layer containing the photosensitive resin composition according to any one of claims 1 to 23.

25. The following method: (1) After the photosensitive resin layer is formed on a flexible substrate, exposure is performed with an energy amount that leaves 15 steps on a Stouffer Industries 41-step step tablet, with a width of 1 inch and a length of 250 mm, to obtain a cured film on the substrate. (2) After exposure, the substrate is immersed in a 1% by weight Na solution at 30°C. ２ CO ３ Develop using an aqueous solution for twice the minimum development time. (3) After development, the substrate is washed with water for twice the shortest development time. (4) After washing with water, the substrate is cut into a 1.2 inch wide piece so that the 1 inch wide cured photosensitive resin layer is located in the center of the width direction, thereby obtaining a sample. (5) Cylindrical Mandrel Method A mandrel test in accordance with JIS K5600-5-1 is carried out on the sample. (6) Determine the smallest mandrel diameter at which cracks are not observed in the cured film, or the smallest mandrel diameter at which peeling of the cured film from the substrate is not observed.

25. The photosensitive resin laminate according to claim 24, wherein the smallest mandrel diameter, as determined by

26. The photosensitive resin laminate according to claim 24, wherein the photosensitive resin layer has a thickness of 10 to 50 μm.

27. the photosensitive resin laminate includes a protective layer on the opposite side of the photosensitive resin layer from the support, 25. The photosensitive resin laminate according to claim 24, wherein the protective layer is a polyethylene terephthalate (PET) film or a biaxially oriented polypropylene (OPP) film.

28. 28. The photosensitive resin laminate according to claim 27, wherein the protective layer has a release layer on a surface thereof.

29. a lamination step of laminating the photosensitive resin layer in the photosensitive resin laminate according to claim 24 on a substrate; an exposure step of exposing the photosensitive resin layer of the photosensitive resin laminate; and a development step of removing unexposed areas of the photosensitive resin layer; A method for forming a resist pattern, comprising:

30. forming a resist pattern on a substrate using the photosensitive resin laminate according to claim 24; forming a conductive pattern by etching or plating the substrate on which the resist pattern has been formed; peeling the resist pattern from the substrate; A method for forming a wiring board, comprising:

31. A photosensitive resin laminate having a support and a photosensitive resin layer containing a photosensitive resin composition, The photosensitive resin composition comprises the following components: (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated bond; and (C) a polymerization initiator; Including, The copolymer (A-1) contains at least the following components: (a1) (meth)acrylic acid; (a2) styrene derivatives; and having a structural unit derived from The content of the (a2) component is 25% by mass or more. Photosensitive resin laminate.

32. The following method: (1) After the photosensitive resin layer is formed on a flexible substrate, exposure is performed with an energy amount that leaves 15 steps on a Stouffer Industries 41-step step tablet, with a width of 1 inch and a length of 250 mm, to obtain a cured film on the substrate. (2) After exposure, the substrate is immersed in a 1% by weight Na solution at 30°C. ２ CO ３ Develop using an aqueous solution for twice the minimum development time. (3) After development, the substrate is washed with water for twice the shortest development time. (4) After washing with water, the substrate is cut into a 1.2 inch wide piece so that the 1 inch wide cured photosensitive resin layer is located in the center of the width direction, thereby obtaining a sample. (5) Cylindrical Mandrel Method A mandrel test in accordance with JIS K5600-5-1 is carried out on the sample. (6) Determine the smallest mandrel diameter at which cracks are not observed in the cured film, or the smallest mandrel diameter at which peeling of the cured film from the substrate is not observed.

32. The photosensitive resin laminate according to claim 31, wherein the smallest mandrel diameter, as determined by

33. 33. The photosensitive resin laminate according to claim 32, wherein the smallest mandrel has a diameter of 6 mm or less.

34. 1% by mass Na at 30°C ２ CO ３ 32. The photosensitive resin laminate according to claim 31, wherein the shortest development time when the aqueous solution is sprayed onto the photosensitive resin layer for a predetermined time is 0.6 to 1.1 seconds per 1 μm of film thickness.

35. The photosensitive resin laminate according to claim 31, wherein the photosensitive resin layer has a thickness of 10 to 50 μm.

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